CA1280768C

CA1280768C - Cyclohexane 1, 3-dione derivatives

Info

Publication number: CA1280768C
Application number: CA000499854A
Authority: CA
Inventors: Richard Burrdidge Warner; Alexander Serban; Lindsay Edwin Cross; Graham John Bird; Graeme John Farquharson; Keith Geoffrey Watson
Original assignee: ICI Australia Ltd
Current assignee: Orica Ltd
Priority date: 1981-11-20
Filing date: 1986-01-17
Publication date: 1991-02-26
Anticipated expiration: 2008-02-26
Also published as: EG17165A; CY1590A; PH21413A; JPH0640993A; DK172078B1; GB2110673A; EP0080301A2; US4760192A; BR8206716A; DK516782A; US4717418A; ES8401931A1; EP0080301B1; PT75876A; EP0080301A3; IE54492B1; JPH0672118B2; IL67126A0; IE822734L; JPH0672128B2

Abstract

ABSTRACT
Cyclohexane-1,3-dione Derivatives Novel compounds of the formula:

Description

3076~3 This application is a division of Serial No.
415,996 filed on November 19, 1982.
This invention relates to organic compounds having biological activity and in particular to organic compounds having herbicidal properties, to processes for the preparation of 6uch compounds, to intermediates useful in the preparation of such compounds and to herbicidal CQmpOsitiOnS and processes utilizing such compounds.
The use of certain cyclohexane-1,3-dione derivatives as grass herbicides is known in the art. For ex~ple, the ~Pesticide Manual~ (C R Worthing Editor, The British Crop Protection Council, 6th Edition 1979) describes the cyclohexane-1,3-dione derivative known oommerclally aB alloYydim-sodium (methyl 3~
~llyloxyimino)butyl7-4-hydroxy-6,6-dimethyl-2-oxocylco-hex-3-ene-car~oxylate) ~nd its use as a grass herbicide.
Tnis compound is disclosed in Australian Patent No 464 655 ~nd its equivalents such as UK Patent No l ~61 170 and US Patent No 3 950 420.
~ore recently, at the 1980 British Cro~
Protection Conference ('1980 Bri~ish Crop Protection Conference - Weeds, Proceedings Vol 1, Research Reports~, pp 39 to 46, Briti~h Crop Protection Cou~cil, 1980), a ,~

new cyclohexane-1,3~dione grass herbicide code named NP 55 (2-(N-ethoxybutrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one) was announced. Thi8 co~pound i8 disclosed in Australian Patent No. 503,917 and its ~quivalent.
As indicated above, both allo~ydim-sodium and NP 55 are grass herbicides, that is, herbicides which selectively control the growth of gra~s weeds ~mono-cotyledonous plants) in broad-leaved crops ~dicotyledon-ous plants).
At the 1978 International Union of Pure and Applied Chemustry Fourth International Congress of Pesticide Chemi~try (~Advance~ in Pesticide Science -Part 2~, pp 235-243, Pergamon Pres6, 1979), in a paper di~cussing the chemical structure and herbicidal activity of alloxydim-sodium~ Iwata~i and Hirono made the following disclosure about the herbicidal ~electivity between wheat and oats of certA~n 5-phenyl substituted cyclohexane-1,3-dione derivatiYes:
~When 6ubstituted phenyl groups were introduced at the C-5 position (Table 6), the selectivity be~ween ~heats and oat6 such ~8 Avena fatua and Avena ativa was observed~ The selectivity was found only in the c~se of para-substit~ent6 ~t the phenyl nucleus and the effect was not found in the case of di~ or tri- ~ubstitution. Even in the para-~ub6tituent~, the degree of activi~y or ~electivity was different.
The be~t result was obtained when the methyl group was introduced at the para-po~ition and the hydroxy or the ~ethoxy derivative save moderately good re~ult~.~
It has now been found that certain S-phenyl ~ubstituted cyclohexane-1,3-dione derivatives in which the phenyl ring ls substituted with more than one ~30~6~3 _ methyl group exhibit particularly useful cereal selec-tive herbicidal activity.
Accordingly the invention provides a compound of formula I:

OR
~CH3)n ~ N_oR2 wherein:
Rl is chosen from the group consisting of: hydrogen;
Cl to C6 alkyl; C2 to C6 alkenyl: C2 to C6 alkynyl;
substituted Cl to C6 alkyl wherein the alkyl group is substituted with a substituent chosen from the group consisting of Cl to C6 alkoxy, Cl to C~ alkylthio, - (Cl to C6 alkoxy)carbonyl, phenyl and substituted phenyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkyl-thio; Cl to C6 (alkyl) sulfonyl; benzene sulfonyl; sub-: stituted benzenesulfonyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio; an acyl group; and an inorganic or organic cation;

R2 is chosen from the group consisting of: Cl to C6 alkyl; C2 to C6 alkenyl; C2 to C6 haloalkenyl; C2 to C6 alkynyl; C2 to C6 haloalkynyl; substituted Cl to C6 alkyl wherein the alkyl group is substituted with _ 4 ~ 7 6~

a substituent chosen from the group consisting of halogen, Cl to C6 alkoxy, Cl to C6 alkylthio, phenyl and substituted phenyl wherein the benzene ring is substituted with from Gne to three substituents chosen from the group consisting of halogen, nitro, cyano, C
to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and C
to C6 alkylthio;

R is chosen from the group consisting of: Cl to C6 alkyl: Cl to C6 fluoroalkyl; C2 to C6 alkenyl; C2 to C6 alkynyl; and phenyl; and n is an integer chosen from 2 to 5.
When in the compound of formula I R is chosen from acyl $he nature of the acyl group is not narrowly critical. Although not intending to be bound by theory, it is believed th~t when Rl is acyl the acyl group is ~ removed in the plant by hydrolysis to give the corres-; ponding compound of formula I in which Rl is hydrogen.
Suitable acyl groups includ~: alkanoyl, for example C2 - to C6 alkanoyl; aroyl, for example benzoyl and substi-tuted benzoyl wherein the henzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio;
and heteroaroyl, for example 2-furoyl, 3-furoyl, 2-; 25 thenoyl and 3-thenoyl.
When in the compound of formula I R is chosen from an inorganic or organic cation the nature of the cation is not narrowly critical. Although not intending to be bound by theory, it is believed that when Rl i~ a cation ~he cation is removed in the plant to give a com-pound of formula I wherein Rl is hydrogen. Suitable inorganic cations include the alkali and alkaline earth 5 ~ 76~3 metal ions, heavy metal ions including ~he transition metal ions, and the ammonium ion. Suitable organic cations include the cation R R R R N wherein R , R , R
and R7 are independently chosen from the group con-sisting of: hydrogen; Cl to C10 alkyl; substituted Clto C10 alkyl wherein the alkyl group is substituted with a substituent chosen from the group consisting of hydroxy, halogen and Cl to C6 alkoxy; phenyl; benzyl; and the groupssubstituted phenyl and substituted benzyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio.
- It should be recognized that when R is hydrogen the compounds of the invention may exist in any one of three tautomeric forms as shown below:

(CH3L~ N-OR (' 33) ..~ ~R3 IIa ~ IIb (CH3)n ~ C_N_oR2 IIc ` - 6 ~076~
Suitable Rl include hydrogen, Cl to C6 alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, C~ to C~ alkanoyl, Cl to C6 alkyl substituted with Cl to C6 alkoxy, Cl to C6 alkylthio, phenyl or substituted phenyl wherein the benzene ring is substituted with from one to three sub-stituents chosen from the group consisting of haloyen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio, benzoyl or substituted benzoyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consist-ing of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio, Cl to C6 (alkyl)sulfonyl and benzenesulfonyl or substituted benzenesulfonyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio, and the group M wherein M is an alkali metal ion.
Suitable R2 include Cl to C6 alkyl, Cl to C6 haloalkyl, C2 to C6 alkenyl, C2 to C6 alkynyl and Cl to C6 alkyl substituted with Cl to C6 alkoxy, Cl to C6 alkylthio, phenyl or substituted phenyl wherein the benzene ring is substituted with from one to three sub-stituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio.
Suitable R3 include Cl to C6 alkyl, C~ to C6 alkenyl and C2 to C6 alkynyl.
Preferred Rl include: hydrogen; C2 to C6 alkanoyl; benzoyl and substituted benzoyl wherein the benzene ring is substituted with from 1 to 3 substituents selected from the group consisting of halogen, nitro, Cl to C6 alkyl and Cl to C6 alkoxy; and an inorganic or organic cation selected from the alkali metal ions, the alkaline earth metal ions, transition metal ions and the _ 7 _ ~ 6~
ammonium ion R4R5R6R7N~ wherein R , R , R and R are independently selected from the group consisting of hydrogen, Cl to C10 alkyl and substituted Cl to C10 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of hydroxy and Cl to C6 alkoxy.
More preferred R include hydrogen, acetyl, tertiary-butyryl, benzoyl, halobenzoyl, methylbenzoyl, methoxybenzoyl, nitrobenzoyl, trimethylbenzoyl, dinitro-benzoyl, the cations of the alkali metals sodium andpotassium; the cations of the alkaline earth metals magnesium, calcium and barium, the cations of the transi-tion metals manganese, copper, zinc, iron, nickel, cobalt and silver, the ammonium ion, and the tri- and tetra-alkyl ammonium ions wherein alkyl is selected from Cl to C6 alkyl and Cl to C6 hydroxyalkyl.
Even more preferred R include hydrogen, benzoyl, sodium and potassium.
Preferred R2 include:Cl to C6 alkyl~ C2 to C6 alkenyl; C2 to C6 alkynyl; Cl to C6 haloalkyl~ C2 to C6 haloalkenyl; Cl to C6 alkyl substituted with Cl to C6 alkoxy; Cl to C6 alkyl substituted with Cl to C6 alkyl-thio; and benzyl and substituted benzyl wherein the benzene ring is substituted with from one to three sub-stituents selected from the group consisting of halogen,nitro and C1 to C6 alkyl.
More preferred R include ethyl, n-propyl, n-butyl, allyl, propargyl, 2-fluoroethyl, 2-chloroallyl, methylthiomethyl, benzyl, halobenzyl, methylbenzyl and nitrobenzyl.
Even more preferred R include ethyl, n-propyl and allyl.
Preferred R3 include C1 to C6 alkyl. More pre-ferred R3 include methyl, ethyl and ~-propyl. Even more preferred R3 include ethyl and n-propyl.
Preferred n is an integer selected from 3 to 5.

~ - 8 - ~ 8076~
Particularly preferred comp~unds of the in-vention include those compounds of formula I in which the benzene ring is substituted in at least the 2-, ~-and 6- positions with methyl groups.
Specific examples of the compounds of the in-vention include those cQmpounds detailed in Table 1 below.
TABLE

(CH3)~ ~ ~ N_oR2 \ R
_ ,, _ . _ poNmO-d (C~3) n Rl R2 R3 . . _ _ _ 1 2, 3- (CH3) 2 ~ C2~5 C2~5 2 2, 4 ( C~ 3) 2 H C2~5 C2H5 3 2, 5 - (CE~3) 2 H C2H5 C2E~5 4 2, 6- ~3) 2 ' El C2H5 C2E~5 3,4~ 3) 2 ~1 C2~5 C2~5 6 3,S~ 3) 2 ~ S~2E~5 C;2~15 7 2 ,4, ~- ~CH3) 3 E~ C2H5 C2H5 8 2t4~5-(CH3) 3 ~ C2E15 C2~5 9 ~ " 3 , S , 6- ( CH 3) 4 B C2~5 C2H5 2, 3 ~ 4, 6- (C}13) 4 E~ C2~5 C2~5 11 3, 4- (CH3) 2 COC6 5 C2~5 C:2H5 12 3,~ 3) 2 t:OCH3 C2H5 C2E15 13 2,5- ~CE~3) 2 COC6H5 C2 5 C;~H5 14 2 3- (CE13) ~2 CC6E~5 C2H5 C;~}~5 2, 4, 6- (CH3) 3 COC6H5 C2~5 C2~5 16 2r 4,6-~CH3) 3 El CH2CH=CH2 n-C3H7 17 2,4,6-~CH3) 3 El CE~2cHzcH2 C2~5 18 ~ ~3) 3 3 C2H5 T~-C3H7 9 ~ 30~6 TABLE 1 Continued .
L~ (CH3) n L Rl ~ L

19 2, 4 ,6--(CH3) 3 H C2H5 CH3 2,4,6-(CH3) 3 H n3 7 C2H5 21 2, 4, 6- ( CH3) 3 H n-C4Hg C2H5 22 2, 4, 6- ( CH3) 3 H a C2~5 23 2,4,6-(CH3) 3 H b C2H5 24 2, 4, 6- (CH3~ 3 H CH2C--CH C2H5 2, 4, 6- (CH3) 3 H CH2CH2F C2H5 26 2,4,6--(CH3) 3HCH2c(cl)=cHr C2~15 27 2, 4, 6- (CH3) 3 H CH2C6H5 C2H5 28 2,4,6-(CH3) 3 H c C2H5 29 2,4,6-(CH3) 3 H d C2 5 2,4,6-(CH3) 3 H e 2 5 31 2,4,6--(CH3) 3H f C2 5 32 2,4,6-(CH3) 3 H g 2 5 33 2,4,6-(CH3) 3 H h C2H5 34 2~4~6-(cH3) 3 H i C2H5 2, 4, 6- (CH3) 3 Hn C4Hg n-c3H7 36 2,4,6-(CH3) 3 H 3 7 37 2,4,6-(CH3) 3 H b n~C3H7 38 2,4,6-(CH3) 3 H CH2c-cH n~C3H7 39 2, 4, 6- (CH3) 3 H CH2CH2F n~C3H7 2,4,6-(CH3) 3 HCH2C(Cl)=CHi In-C3H7 7~

TABLE 1 - continued ( CH 3) D R R k _ 41 2,4,6-(CH3) 3 H c n~C3H7 42 2,4,6-~CH3) 3 H d n~C3H7 43 2,4,6-(CH3) 3 Na~C2H5 C2H5 44 2, 4 , 6 - ( CH 3) 3 i C2H5 C2H5 2, 4, 6- (CH3) 3 k C2H5 C2H5 46 2,4,6-(CH3) 3 1 C2H5 C2H5 47 2, 4 ,6- (CH3) 3 Na~CH2cH=cH2 C2H5 4 8 2, 4, 6 - ( CH 3) 3 COC6H5 CH 2CH=CH2 C2~5 49 2,4,6-(C~3) 3 COC6H5 CH C---CEI C2~5 2, 4, 6- (CH3) 3 COC6H5 C2H5 n-C3H7 51 2, 4, 6- ( CH 3) 3 CC6E15 CH 2CH=CH 2 n~~3H 7 52 2, 3, 4--(CH3) 3 H C2H5 C2H5 53 2, 3, 5--(CH3) 3 H C2H5 C2H5 54 3,4,5--(CH3) 3 H C2H5 C2H5 2, 3, 4, 6- (CH3) 4 H C2H5 n~C3H7 56 2, 3, 4, 6- ( CH 3) 4 H CH2cH=cH2 C2H5 57 2,3,~,6-(CH3) 4 HCH2CH-CH2 n~C3H7 58 2, 3, 4, 6- (CH3) 4 COC6H5 C2H5 C2H5 59 2, 3,4 ,s-(CH3) 4 Na~C2H5 C2H5 2~3~4~5~6-(cH3) 5 H C2H5 C2H5 61 2,3,4,5,6--(CH3) 5 HCH2cH=cEl2 C2H5 62 2,3,4,5,6-(CH3)5 H C2H5 n~C3H7 _ 7~
TABLE 1 - continued _ _ _ _ ~ pound ( 3)n Rl R2 R3 _ 63 2,3,4,5,6-(CH3)5 H CH2CH=CH2 n~C3H7 64 2,3,4,5-(CH3)4 H C2H5 C2H5 3,4-(CH3)2 H n C3 7 C2H5 66 3,4-(CH3)2 H CH2CH=CH2 C2H5 67 3,4-(CH3)2 H C2~5 n C3 7 68 3,4-(CH3)2 H n-C3 7 n~C3H7 69 3,4-(CH3)2 H CH2CH=CH2 n~C3H7 2,3,4,5,6-(CH3)5 H C2H5 CH3 71 2,3,6-(CH3)3 H C2H5 C2H5 72 2,3,4,5,6-(CH3)5 Na C2~5 n C3 7 73 2,3,4,5,6-(CH3)5 COC6H C~5 n C3 7 74 2 3,4,6-(CH3)4 H CB2CH2F n~C3H7 2,3,4,5,6-(CH3)5 H CB2CH2F n~C3H7 76 2,3,4,5,6-(CH3)5 H CB2CH2F C2H5 77 2,3,4,5,6-(CH3)5 H CB3 n C3H7 78 2~3~4~5~6-(cH3)5 Na~ C2H5 C2H5 79 2,3,4,5,6-(CH3)5 H n C3 7 n~C3H7 2,3,4,5,6-(CH3)5 H CH3 C2H5 Bl 2,3,4,5,6-(CH3)5 COC6H5 C2H5 C2~5 82 2,3,4,5,6-(CH3)5 H ¦CH2C(C1)=CH2 n~C3H7 83 2,3,4,5,6-(CH3)5 H ¦ a C2H5 2,3,4,5,6-(CH3)5 1~ Cu ~I C2H5 n~C3H7 2~76~

TABLE 1 - continued _ pONmond (CH3) n Rl R2 R3 . _ ~ -2,3,4,5,6-(CH3)5 3~ Ni~3 C2H5 n~C3H7 86 2,3,4,5,6-(CH3) 5 H CH2SCH3 C2H5 87 2,5-(CH3) 2 H C2H5 C6H5 88 2, 4, 6- (CH3) 3(n-C4Hg) C2H5 C2H5 89 2 ,4, 6- (CH3) 3 m C2H5 C2H5 2 , 4 , 6- ( CH 3) 3 n C2H 5 C2H 5 91 2,4 ,6- (CII3) 3 C2H5 C2H5 92 2, 4, 6- (CH3) 3 P C2H5 C2H5 93 2,4,6-(CH3) 3 C 3 C2H5 C2H5 94 2, 4, 6--(CH3) 3 ~ C2H5 C2H5 2, 4, 6- (CH3) 3 r C2H5 C2~5 _ _ ~

~8~76 - Footnotes to Table 1 -a - trans C 2 3 b - CH 2CH 2CH C~l 2 c - CH2C6 4 d - C~12C6H4Br-4 e - CE12C6H4F-4 f C 2 6 4 3 g - CH2C6H4N2-4 h - CH2C6H4Cl-3 - CH2C6H3Cl2-2, 4 CoC6H4N02-4 k - COC6 4 2 - COC6E~3(r~02) 2-3~5 m - COC6H4CH3 4 n - COC~H2~CB3~ 3-2,4,~
o _ COC6H40CH3--4 p - COC6H4Cl-4 ~ COC(CH3) 3 r - CH2COOCH2CH3 ~'~8~76~
-14. -The compounds o~ th~ inventi~n ~ay be prepared by a variety of ~ethods and in a further aspect the the invention proYides methods for the preparation of compounds of formula I.
Conveniently the prepara~ion of the compounds of the invention can be considered in three or four parts.
Part A involves the formation of a 5-(substitu-ted phenyl)cyclohexane-1,3-dione of formula IX. This reaction may be carried out in a two ~tep process by condens~ng a benzaldehyde derivative of formula V wi~h acetone to ~orm a ketone of formula Vl, which i~ in turn condensed with a malonic acid ester of formula VII
to give a 5-(substituted phenyl)cyclohexane-1,3-dione o~ formula IX~ either with or without th0 isolation of the lntermcdi~te of ormu1 VIII.
A.ternatively, this preparation may be carried out in a two step process by condensing a benzaldehyde derivative of formula V with a malonic acid ester of formula YII to give a benzylidenemalonate deri~ative - of formula X which is in turn condensed with an aceto-acetic acid ester of formula XI to give a 5-(substituted phenyl)cyclohexane-1,3-dione of formula IX, either wi~h or without i~olation of the intermediate of formula : 25 XII.
In a further alternative process this preparation may be carried out by condensing a cinnamate of formula XXI with an acetoacetic acid ester of formula XI to give a 5-~substituted phenyl)cyclohexane-1,3-dione of formula IX, either with or without isolation of the intermediate of formula VlII.

The abov~ reaction sequences are set out in SCHEME A parts (i), (ii) and (iii) respectively below, wherein R represents a Cl to C6 alkyl group.

EME A
(i) ~CH3) ~ CHO + CH3cocH3 ~ ~ H=CH-COCH3 V VI

3 ~ C~-C~-COCB3 ~ CH2~C02R)2 VI VII

~ (CH3~ n VIII

(C~3) ~ ~ ~C~3) ~

CO2~
VIII IX

~'29~3~76~
- lG -($i) ~CH3)~3 CHO + CE12(C02R) ;!

V VII

3 ~3 CH=C (C2~) 2 ~=C(~023R) 2 ~ C~3~2 X XI

1) R~e (C~31 X:tI

t~2R O O
(CH3)~$ ~ (CH3)~

XII IX

17 ~ 76~3 (iii) ( CH 3 )n~3 CH=CH-C02R +CH 3COCH 2C02R

XXI XI
o 1) ROe ~ 3) n ~ /~
2) H~
' C02R O
VIII

H3) n~_~ (CH3)~

CO2~
YIII IX

Part B ~nvol~e~ th~ ~cylation of a oompou~d of ~or~ula IX to g~ve a 2-acyl-5-(~ub~tuted phenyl~-cyclohexane-1,3-dione of formula XIII . This reaction 5 may be carried out by reacting a 5-(~ubstituted phenyl)-cyclohexane-1,3-dione of formula IX with:
(iv) a mixture of an acid anhydride of formula XIV
~ ~nd either a ~lt of that acid or an alkoxide : ~alt ~herei~ ~ iB an alkali me~al ion and R i~
C~ to C6 alkyl;
(v) n nixture of ~n acid anhydride of formula XIV and the corresponding acid;
(vi) an acid halide of formula XV;

` - 18 ~ 7~
~vii) a mixture of an acid halide of formula XV
and the corresponding acid; or (viii) an alkali metal or alkaline earth metal hydride followed by reaction with an acid anhydride of formula XIV or an acid halide of formula XV.

AlternatiYely this re~ction may be carried out by:
(ix) re~cting a 5-(substituted phenyl)cyclohexane-1,3-dione of formula IX with ar. acid halide of formula XV in the presence of pyridine to give an intermediate O-acyl deri~ative of formula XVI; a~d then:
(x) reac~ing the intermRdiate of formula XVI with a Lewis ~cid catalyst;
(xi) reac~i~g the intermediate of formula XVI with the corTesponding acid vf the acid halide of ' formula XV; or (xii) reacting the intermediate of formula XVI with imidazole .
Each of the~e reaction~ i8 outlined in ~C~EME B
Ibelaw ~hereln hal repre~ents halogen.

l'~t~ 76~3 ( iv) (C~3)~ /~ 3 C ~ ,~ + (R CO) 2 O
IX XIV

1) R3Co2M or 3 ~ ~ 3 XIII

(v) //o ~3)~ ~ ~R3Co) 2 IX XIV

R3co2 ~ 3~ ~ 5) \J~ \R3 O
XlII

'. '. , ~,~,a~7~8 ~ 20 --tvi) ~

3 ~ ~ R COhal IX XV

OH
Lewis acid ~ 3 ~ \R3 XIII
( vii ) + R COhal lX; XY
o~
R3Co2 ~ 3) ~ C~3 XIII
(viii) (CH3)n y3{~ + (R3Co2)0 or R3COhal IX O XIV XV

. .
e ( CH3) n~C~/ o3 2 ) XIV or XV

XIII

~Z80768 (ix) b IX XV
pCoR3 (CEI3)~ .

XVI

(x) ,OCOR
(CH3) ~
~ ' X~

Lewl~ acid~ ~ ~R3 XIII
xi ) oR3 (CH3) n~
O
XVI

R C02il/!i ~_C~s3 ~III

7~

(xii) pCoR3 (CH

XVI

Lmidazole ~ 3 ~ C\ o3 XIII

Part C involves the formation of a compound of the in~ention of formula I wherein Rl is hydIogen~
that i8 a co~pound of formula II. This reaction may be carried out either:
~xiii) by reacting a compound of formula XIII with an alkoxyamine derivative of formula XVII to give a compound o~ ~ormula II; or (xiv) by reacting a ccm~ound of formula XIII with hydroxylamine to give an intermediate oxime derivativ2 of formula XVqII and reacting the oxime derivative of formula ~VIII wi~h an alkylating agent of formula XIX to give a compound of formula II.
The~e reaction ~equences are 6et out in ~C~EME
C below wherein L i~ a good leaving group ~uch as, for e~ample, chloride, bromide, iodide, sulfate, nitratej methyl sulfate, ethyl ~ulfate, tetrafluoroborate, hex~fluorophosphate, hexafluoroantimonate, ~ethane-~ulfonate, fluorosulfonate, ~luoromethanesulfonate and trifluoromethanesulfonate.

,. : - . ...

~X8~376~

_ 23 --SCHE~
( xiii ) L~C~ 3 t H 2NOR2 XIII XVII

(CH3~ n~l~-OR2 II

( xiv) 3 ~ C~ + El 2N

XIII

~Ci33)~ ~I~

XVIII

` ~L28~)7~3 _ 24 -(CH3) ~ C~ R3 XVIII ~IX

~ 3) ~ ~ ~-OR

Compounds of the invention of formula I where-- in Rl is an acyl or a sulfonyl group may be prepared from compounds o~ the invention of formula I wherein R is hydrogen, that is, compounds of formula II, by etherifi-cation, acylation, or sulfonylation as requiredO This reaction is outlined in SCHEME D below.

8C~EME ~
(C~33) ~ ~ -OR

II XX

3 ~ C~

I
}

)76~
~5 -Compounds of the invention of formula I
wherein Rl is an inorganic or organis cation may be pre-pared from the compou~ds of ~he invention of formula I
wherein Rl is hydrogen, that is, compounds of formula II, by reacting said compounds of formula II with an in-organic or organic salt. For example, the compounds of formula I wherein Rl is an alkali metal ion may be pre-pared by reacting the appropriate compound of formula II
with the appropriate alkali metal hydroxide or alkoxy-late. The compounds of formula I wherein Rl is atransition metal ion or an organic cation may similarly be prepared by reacting the appropriate compound of formula II with an appropriate transition metal salt or organic base. Alternatively, the compounds of formula I
wherein Rl is a transition metal ion or an organic cation may be prepared by reacting the appropriate com-pound of formula I wherein Rl is an alkali metal ion with an appropriate transition metal salt or organic ~alt.
Accordingly, ln a ~ur~her aspect the $nvent~on provide5 a proc~s for the preparation of a conpound of ~ormula I, wherein Rl, R2 and R3 are as hereinbe~ore defined, which proce~s comprises:
a) reacting a benzaldehyde derivative of formula V with acetone to give a ketone aerivative of formula VI
and reacting the ketone derivative of formula Vl with a malonic acid e~ter of formula VII, wherein R
ie Cl to C6 ~lkyl, to give a 5-(~ubstituted phenyl1-cyclohexane-l,3-dione derivative of formula IX; or reacting a benzaldehyde derivative of formula V
~ith a malonic ~cid ester of formula YII to give a benzylidenemalonate derivative of formula X and reacting the benzylidenemalonate derivative of ~ormula X ~lth an acetoacetic acid e~ter o~ ~ormuls ~L2~768 XI, wherein R i~ Cl to C6 alkyl, t~ gi~e a 5-(~ubstituted phenyl)cyclohe~ane-1,3-dione derivative of ~on~ula IX; or reacting a cinnamate of formula XXI, wherein R is Cl to C6 alkyl, with an acetoacetic acid ester of formula XI, wherein R is Cl to C6 alkyl, to give a 5-(substituted phenyl)cyclohexane~l,3-dione deriva-tive of formula IX;

b) ~cylating ~he 5-tsubstituted phenyl)cyclohexane-1,3-dione derivative of formula IX with an acid anhydride of formula XIV or an acid halide of formula XV to gi~re a 2-acyl-5-~substituted phenyl)cyclohexane~lt3-dione derivative of ~ormula XIII;
c~ reacting the 2-acy1-5-(sub~tituted phenyl) cyclohexane-l, 3-dione derivative of formula XIII
with an alko~yamine derivative of formula XVII to ~ve ~ ~ompound of the inv~tion of formula II or reacting the 2-acyl 5-(~ub t~tuted p~nyl)cyclo-hexane-1,3-dione deri~ative of formula XIII with hydroxylamine and alkylating the oxime intermediate of formula XVIII with an alkylating agent of formula XIX, wherein L is a good leaving group, to give : a compound of the invention of formula II; and optionally d) reacting the compound of the invention of formula II with a compound of formula XX, wherein L i6 a good leaving group, or reacting the compound of the invention of formula II with an inorganic or organic base or salt, to give a compound of the invention of formula I.
.~

8076~3 _ ~7 -Certain of the intermediate compounds of formulae VI, VIII, IX, X, XII, XXI, XIII, XVI and XVIII
are novel compounds and therefore as a further embodi-ment the invention provides novel compounds of formulae S VI, VIII, IX, X, XII, XXI, XIII, XVI and XVIII, wherein the substituents are as hereinbefore defined, and pro-cesses for the preparation thereof.
The compounds of formula I are active as herbicides against monocotyledonous weeds, wild grasses, and in particular are selectively active against diffi-cultly controllable wild grasses in crops of cultivated plants. The compounds of the invention are especially useful in the control of wild grasses such as wild oats and rye grass in crops of cultivated monocotyledonous plants such as wheat, barley and other varieties or cereals.
Accordingly, in yet a further aspect the in-vention provides a process for controlling monocotyle-donous weeds in cultivated crops, especially wild grasses in cereal crops such as wheat and barley, which process comprises applying to the crop, or to the growth medium of the crop, a compound of formula I, as herein-before defined, in an amount sufficient to severely damage or kill the weeds but insufficient to damage the crop substantially.
As hereinbefore indicated, certain cyclohexane-1,3-dione derivatives, such as those disclosed in Australian Patent 464,655 and Australian Patent No.
503,917 and numerous other patents and patent applications, are known to be general grass herbicides which show no useful cereal selectivity.
Moreover, it is known from the teaching of Iwataki and Hirono (~Advances in Pesticides Science - Part 2", pp 235-243, Pergamon Press, 1979) that some cereal selectivity is observed in such cyclohexane-1,3-dione derivatives when a phenyl group substituted in the para-8Ç[376~3 position is introduced into the 5-positicn of the cyclo-hexane ring but that "The selectivity was found only in the case of para-substituents at the phenyl nucleus and that the effect was not found in th~ case of di- or tri-substitution". Therefore, it is completely unexpectedto find that the cyclohexane-1,3-dione derivatives of the present invention, which have, located in the 5-position of the cyclohexane ring, a phenyl group which is in turn substituted with from two to five methyl groups, are cereal selective herbicides which effectively control monocotyledonous weeds such as wild oats and rye grass in crops of sensitive , cultivated monocotyledonous plants such as wheat and barley. It is even more sur-prising to find that those cyclohexane-1,3-dione deriva-tives of the present invention which have, located in the5-position of the cyclohexane ring, a phenyl group which is in turn substituted with methyl groups in at least the 2-, 4- and 6- positions, are highly active against monocotyledonous weeds such as wild oats and rye grass at very low rates of application and at the same time are very safe on wheat, a sensitive, cultivated mono-cotyledonous plant.
The compounds of formula I may be applied directly to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emergence application)~ Howeverl the compounds are, in general, more effective when applied to the plant post-emergence.
The compounds of formula I may be used on their own to inhibit the growth of, severely damage, or kill plants but are preferably used in the form of a com-position comprising a compound of the invantion in ad-mixture with a carrier. Therefore, in yet a further aspect the invention provides plant growth inhibiting, plant damagingt or plant killing compositions comprising a compound of formula I as hereinbefore defined and an inert carrier therefor.

1 ZB~76~
- 2~ -The compositions of the present invention may be in the form of solids, liquids or pastes. The com-positions include both dilute compositions which are ready for immediate use and concentrated compositions which may require dilution before use. Therefore, the concentration of the active ingredient in the com-positions of the present invention will vary depending on the type of formulation and whether the composition is ready for use such as, for example, a dust formulation or an aqueous emulsion or whether the composition is a concentrate such as, for examplet an emulsifiable con-centrate or a wettable powder, which is suitable ~or dilution before use. In general the compositions of the present invention comprise from 0.01% to 99% by weight of active ingredient.
The solid compositions may be in the form of powders, dusts, pellets, grains, and granules wherein the active ingredient is mixed with a solid diluent.
Powders and dusts may be prepared by mixing or grinding the active ingredient with a solid carrier to give a finely divided composition. Granules, grains and pellets may be prepared by bonding the active ingredient to a solid carrier, for example, by coating or im-pregnating the preformed granular solid carrier with the active ingredient or by agglomeration techniques.
: Examples of solid carriers include: mineral earths and clays such as, for example, kaolin, bentonite, kieselguhr, Fuller's earth, Attaclay, diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, :Lime, calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulfate, gypsum, calcium sulfate, pyrophyllite, silicic acid, silicates and silica gels; fertilizers ~uch as, for example, ammonium sulfate, ~mmonium phosphate, ammonium .nitrate and urea; natural products of vegetable 3S origin such as, for example, grain meals and flours, bark meals, wood meals, nutshell meals and cellulosic powders;

` ` ` ~IL28 and synthetic polymeric materials such as, for example, ground or powdered plastics and resins.
Alternatively,the solid compositions may be in the form of dispersible or wettable dusts, powders, granules or grains wherein the active ingredient and the solld carrier are combined with one or more surface active agents which act as wetting, emulsifying and/or dispersing ~gents to facilitate the dispersion of the active ingredient in liquid.
Examples of surface active agents include those of the cationic, anionic and non-ionic type. Cationic surface active agents include quaternary ammonium com-pounds, for example, the long chain alkylammonium salts such as cetyltrimethylammonium bromide. Anionic surface 15 active agents include: soaps or the alkali metal, alkaline earth metal and ammonium salts of fatty acids;
the alkali metal, alkaline e~r~h metal and ~moni~m s~lts of ligninsulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids including ~ 20 the salts of naphthalenesulfonic acids such as butyl-i naphthalenesulfonic acid, the di- and tri- isopropyl-naphthalenesulfonic acids, the salts of the condensation products of sulfonated naphthalene and naphthalene der-ivatives with formaldehyde, the salts of the condensation 25 products of sulfonated naphthalene and naphthalene der-ivatives with phenol and formaldehyde, and the salts of r alkylarylbenzenesulfonic acids such as dodecylbenzene-sulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of the long chain mono esters of sulfuric 30 acid or alkylsulfates such as laurylsulfate and the mono e6ters of sulfuric acid with fatty alcohol glycol ethers.
~onionic surface active agents include: the condensation products of ethylene oxide with fatty acohols such as oleyl alcohol and cetyl alcohol; the conde~sation pro-35 ducts of ethylene oxide with phenols and alkylphenols such as isooctylphenol, octylphenol and nonylphenol; the 8V7~

condensation products of ethylene oxide with castor oil;
the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate, and their condensation products with ethylene oxide;
ethylene oxide/propylene oxide block copolymers; lauryl alcohol polyglycol ether acetal; and the lecithins.
The liquid cornpositions may comprise a solu-tion or dispersion of the active ingredient in a liquid carrier optionally containing one or more surface active agents which act as wetting, emulsifying and/or dispers-ing agents. Examples of liquid carriers include:
water; mineral oil fractions such as, for example, kerosene, solvent naph~ha, petroleum, coal tar olls and aromatic petrolewn fractions; aliphatic, cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin, cyclohexane, toluene, the xylenes, tetrahydronaphthalene and alkylated naphthalenes; alcohols such as, for ex-ample, methanol, ethanol, propanol, isopropanoll butanol, cyclohexanol and propylene glycol; ketones such as, for exarnple, cyclohexanone and isophorone; and strongly polar organic solvents such as, for exarnple, dimethylformamlde, dimethylsulfoxide, N-methylpyrrolidone and sulfolane.
A preferred liquid composition comprises an aqueous suspension, dispersion or emulsion of the active ingredient which is suitable for application by spraying, atomizing or watering. Such aqueous compositions are generally prepared by mixing concentrated compositions with water. Suitable concentrated compositions include emulsion concentrates, pastes, oil dispersions, aqueous suspensions and wettable powders. The concentrates are usually required to withstand storage for prolonged periods and after such storage to be capable of dilution with water to form aqueous preparations which rernain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The con-~ 8~)76!3 centrates conveniently contain from 20 to 99%, prefer-ably 20 to 60%, by weight of active ingredient.
Emulsion or emulsifiable concentrates are con-veniently prepared by dissolving the active ingredient s in an organic solvent containing one or more surface active agents. Pastes may be prepared by blending the finely divided active ingredient with a finely divided ! solid carrier, one or more surface active agents and optionally an oil. Oil dispersions may be prepared by grinding together the active ingredient, a hydrocarbon oil, and one or more surface active agents. Aqueous suspension concentrates may conveniently be prepared by ball milling a mixture of the active ingredient, water, at least one surface active agent and preferably at least one suspending agent. Suitable suspending agents in-clude: hydrophilic colloids such as, for example, poly-(N-vinylpyrrolidone), sodium carboxymethylcellulose and the ~egetable gums gum acacia and gum tragacanth;
hydrated colloidal mineral silicates such as, for ex-ample, montmorillonite, beidellite, nontronite, hectorite,saponite, sauconite and bentonite; other cellulose deri-vatives; and poly(vinyl alcohol). W~ttable powder con-centrates may conveniently be prepared by blending to-gether the active ingredient, one or more surface active agents, one or more solid carriers and optionally one or more suspending agents and grinding the mixture to give a powder having the required particle size.
The aqueous suspensions, dispersions or emulsions may be prepared from the concentrated com-positions by mixing the concentrated compositions withwater optionally containing surface active agents and/or oils.
It should be noted that the compounds of the invention of formula I wherein Rl is hydrogen are acidic.
Therefore, the compounds of formula I may be formulated and applied as the salts of organic or inorganic bases.

In formulating and employing the compounds o formula I
in the form of their salts either the salts per se, that is the compounds of formula I wherein R is an inorganic or an organic cation, may be used in the formulation or the compounds of formula I wherein Rl is hydrogen may be used in the formulation and the salts generated in situ by the use of the appropriate organic or inorganic base.
The mode of application of the compositions of the invention will depend to a large extent on the type of composition used and the facilities available for its application. Solid compositions may be applied by dust-ing or any other suitable means for broadcasting or spreading the solid. Liquid compositions may be applied by spraying, atomizing, watering, introduction into the irriyation water, or any other suitable means for broad-casting or spreading the liquid.
The rate of application of the compounds of the invention will depend on a number of factors includ-ing, for example, the compound chosen for use, the identity o~ the plants whose growth is to be inhibited the formulations selected for use and whether the comp-pound is to be appli~d for foliage or root uptake. As a general guide, however, an application rate of from 0.005 to 20 kilograms per hectare is suitable while from 0 01 to 5.0 kilograms per hectare may be preferred.
The compositions of the in~ention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activi~y. For example, as herein-before indicated the compounds of the invention are ingeneral substantially more effective against mono-cotyledonous plants or grass species than against di-cotyledonous plants or broad-leaved species. As a result, in certain applications the herbicidal use of the com-pounds of the invention alonemay not be sufficient to pro-~307~i8- 34 -- tect a crop. Accordingly in yet a still further embodiment the invention provides a herbicidal composi-tion comprising a muxture of at least one herbicidal compound of formula I as hereinbefore defined with at least one other herbicide.
The other herbicide may be any herbicide not having the formula I. It will generally be a herbicide having ~ co~ple~entary action~ For example, one pre-ferred class is of mixtures comprising a herbic~de acti~e against broad-leaved weeds. A second preferred class i~
of mlxtures comprising a contact herbicide.
Examples of useful co~plementary herbicides include:
A. benzo-2,1,3-thiadi~zin-4-one-2,2-dioxides such as 3-i~opropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide , ~common name bentazon);
s B~ horm~ne herbicides and in particular the phenoxy-alkanoic acids su~h a~ 4-chloro-2-methylphenoxy ~ aoetic acid (common nam2 kCPA), 2-(2,4-dichloro-j 20 phenoxy)propionic acid (oommon name dichlorprop), 2,4,5-trichlorophenoxyacetic acid Sco n name 2,4,5-T~ (4-chloro-2-methylphenoxy)butyric acid (com~on n~e ~CPB), 2,4~dichlorophenoxyacetic acid (common namR 2,4-D)~ 4-(2,4-dichlorophenoxy)butyric acid (oomm~n name 2,4-DB~, 2-(4-chloro-2-methyl-phenoxy)propi~nic acid (co n na~e mecoprop), and their derivatives (eg ~alts, esters, smides and the lilc~ );
C. 3~ halophenoxy)phenyl7-1,1-dialkylurea~ ~uch as 3-~ -chlorophenoxy)ph~nyl7-1,1-dimethylurea ~oommQn n~me chloroxuron);
D. dinitrophenol6 and their derivatiYes (eg acetates) uch ~8 2-~athyl-~,6-dinitrophenol (common name DWOC), 2-t-rti~rybutyl-4,6-dinltnoph~nol (oo n ~ Z~30768 ~me dinoterb), 2-secondarybutyl~,6-din~tr~phenol ~c~mmon n~ no~eb) and it~ ester dino~b ~c~t~e~
. dinitroaniline herbicides such as N',N'-diethyl-2,6-ainitro-~-trifluorGmethyl-m-phenylenediæmine ~ocmmon name din$tra~;ne), 2, 60d~ nit~o-N,N-dipropyl-4-trifluoromethylaniline (common name trifluralin) and 4-methylsulfonyl-2,6-dinitro-N,N~dipropylaniline (common name nitralin);
F. phenylurea herbicides ~uch as N'-~3,4-dichloro-phenyl)-N,N-dimethylurea (common name diuron) and N,N-dim2thyl-N'-~-(trifluoromethyl)phenyl7urea (co~non name fluometuron);
G. phenylcarbamoyloxyphenylcarbamates such as 3~
~metho~ycarbonyl)aminQ7phenyl (3-methylphenyl~-rarbamate (comm~n name phenmedipham) and 3-~ethoxy-carbonyl)amino7phenyl phenylcarbamate (comm~n name - desmedipham)~
. 2-phenylpyrid~zin-3-ones ~uch as 5-amino-4-chloro-2-phenylpyridazin-3-on~ (oommon n~me pyrazon);
20 I. uracil herbicides 8uch a~ 3-cyclohexy1-5,6-trime~hyleneuracil (common name lenacil), 5-br,omo-3-~ec-buty1-6-methyluracil (common name bromacil) and 3-tert buty-5-chloro-6-methyluracil (common name terbacil) ~
25 J. ~riazine herbicides BUCh as 2-chloro-4-ethylamino-6-(~o-propy1amino)-1,3,5-triazine (comm~n name i ~trazine), 2-chloro-4,6-di(ethylamino)~1,3,5-triaz~ne (oomm~n name ~imazine) ~n~ 2-azido-4-~i~o-propylamino)-6-methylthio-1,3,5-triazine (oommon nam~ ~ziproptryn~);
lkvxy-2-alkyl-3-phenylurea herbicides such as 3-~3,~-dichlorophenyl)-1-methoxy-1-methylurea t oommon name linuron), 3-(~chlorophenyl)-1-a~thoxy-l-~ethylure~ ~o~mon ~amæ mQnolinuron) an~

1.2~30~i8 3-(--brom~ chlo~oph~nyl)-1-me~hoxy-1 ~e~hylur~a (oommon name chlorobromuron);
. thiolcarbamate herbicides such as S-propyl dipropyl-thiocarbamate (comm~n name verolate);
. 1,2,~-tria~in-5-one herbicidRs uch a~ ~-amin~-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (co n name met d tron) and ~-am~no-6-tert-butyl-4,5-dihydro-3-methylthio-1,3,4-triazin-5-one (common name metribuzin);
N. benzoic acid her~icides ~uch as 2,3,6-trichloro-benzoic acid (common name 2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common nam~ dicamba) and 3-amino-2,5-dichlorobenzoic acid ~common name chloramben).
O. anilide herbicides ~uch as N-butoxymethyl~-chloro-2',6'-diethylacetanilide ~common name butachlor), the corresponding ~-methoxy compound (common name alachlor), the corresponding N-i~o-propyl compound (comm~n Dam2 propachlor~ and 3',4'-dichloro-; propionanilide (oommon name propanil);
: P. dihalobenzonitrile ~erbici~es such a~ 2,6-dichloro-benzonitrile (co~mon name dichlobenil), 3,5-dibrom4-4-hydroxybenzonit$ile (comm~n ~ame bromoxynil) and : 3,5-diiodo-4-hydro~ybenzonitrile (common name . ioxynil).
Q~ haloalkanoic her~i~ides ~uch as 2,2-di~hloro-propionic acid ~o~mmon name dalapon), trichloro-acetic acid (oomn~n na~e TCA) and ~alt~ thereof;
R. diphenylether herbicide~ ~uch ~8 4-nitrophenyl 2-~itro~4-trifluoromethylphenyl ether ~comm~n nam~
~luorodifen), methyl 5-(2,4-dichlorophenoxy)-2-~itr~benzo~te (oo n name bif~nox), 2-n~tro-5-~2-7~i~

trifluo~2thylphenoacy) benzoic llcid and 2-c2~10ro-4-trif~20romethylphenyl 3-e'choxy-4 nitro-pllenyl ~ther;
S. N-(heteroarylaminocarbonyl)benzenesulfonamides such as 2-chloro-N-~4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl7benzenesulfonamide (commonly known as DPX 4189); and T. ~i~cellaneo~ herbicides including N,N-di~ethyl-diphenylacetamide tcommon name diphenamud), N ~1-n~phthyl)phthalhmic ~cid ~oomm~ ~ame naptalam) ~nd 3-amino-1,2,4-triazole~
Exa~ples of useful contact herbicides include:
V ~ipyridylium herbicides such as those in which the active entity is the l,l'-dimethyl-4,4'-dipyridylium ion Icomm~n name paraquat) and those in which the active entity is the l,l'-ethylene 2,2'-dipyri~ylium iorl ( common name diquat);
V organoarsenical herbicides uch as monosodium methanearsonate ~ co~on name ~ ); and 20 W amino acid herbicides ~uch a~ N- tphosphonomethyl) -glycine (comrnon name glyphosate) and its salts and es ters .

7~8 .

The invention is now illustrated by, but in no way limited to, the following Examples~
Example 1 2~ (Etho~imino)propyl7-3-hydr ~ ylcyclohex-2-en-1-one (7) ~i) An aqueous solution of 1~ ~odium hydroxide (29.5 ml) was added dropwise over a period of 5 minutes to a suspension of mesitylaldeh~de (10.0 g; 68 mmole~ in acetone (50 ml) and water (50 ml). The mixture was ~tirred at a tempera-ture of 65C for a period of 1~ hours and then was extracted with dichloromethane (200 ml). The organic extract was washed several times with water, dried over anhydrous sodium sulfate, and the solvent was removed by evaporation under reduced pressure using a rotary evaporator.
The product 1-(2,4,6-trimethylphenyl)but-1-en-3-one, a viscous oil, solidified on standing to ; give a white solid ~11.5 g; 90%~, mp 64C.
Prston magnetic resonance spectrum (CDC13; ~ in ppm): 2.25 (12H, m); 6.30 (lH, d); 6.88 (2H, s);
7.64 (lH, d).
(ii) Diethyl malonate (10.1 g 60 mmole) was added : to a solution of ~odium m~tal (1.4 g; 60 mmole) ~n anhydrous absolute ethanol (50 ml) and the mixture was heated to reflux temperature. A
; mixture of 1-(2,4,6-trimethylphenyl~but-1-en-3-one (11.4 g; 61 mmole) in anhydrous absolute ethanol ~50 ml) was added over a period of 2 minutes and the mixture was heated under reflux for a period of 2 hours. An aqueous solution of sodium hydroxide (7.3 g; 180 mmole in 100 ml o~ water) was added and the mixture was heated under reflux for a further 4~ hours. The solution 076~3 was poured into water (200 ml) and the aqueous mixture was extracted twice with ethyl acetate ~100 ml). me aqueous phase was acidified with concentrated hydrochloric acid and warmed gently until the evolution of carbon dioxide eea~ed.
The aqueous mixture was extracted with ethyl acetate, dried over anhydrous sodium sulate, and ~he solvent was r~moved by evaporation under reduced pressure using a rotary evaporator. The product~ 3-hydroxy-5-mesitylcyclohex-2-en-1-one, was obtained aB a pale yellow ~olid (10.9 g;
77.4%), mp 165C. ~roton magnetic resonance spectrum (D6-dimethylsulfoxide; ~ in ppm):
2~0-4.1 (1~, m); 5.-2-(lH, s); 6.8 (2H, s);
11.2 (lH, br.s.1.
(iii) Propionic anhydride (15.0 ml) w~s added cautiou~ly to freshly prepared sodium methoxide (0.47 g; 9 mmole). On completion of ~he reaction 3-hydroxy-5-m~sitylcyclohex-2-en-1-one (5.0 g;
22 mmole) was added a~d the reaction mixture was heated under reflux at a temperature of 160C
for a period of 2 hours. The excess propionic anhydride was re~oved by evaporation under re-duced pressure u~ing a rotary evaporator.
Aqueous 30% ~odium hydroxide ~olution (50 ml) was added to the residue and the mixture wa6 heated under reflux for a period of 1 hour with vigorou~ stirring. After cooling the m~xture was acidl~ied with concentrated hydrochloric abid and the ~queous mixture was extracted with dlchlorom~thane. The organ~c extract~ were dried over anhydrou~ sodium sulfate and the ~olvent was removed by evaporation under reduced pressure using a rotary evaporator. The product, ,, )76~3 a brown oil, was purified by hromatography over silica gel (eluant dichlorome~hane~ to give 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en 1-one (3.17 g; 50.2~) as a pale yellow oil. Proton magnetic resonance ~pectrum (CDC13; ~ in ppm):
1.60 (3H, t, J=8Hz); 2.24 (3H, 8); 2.37 (6H, s);
2.64-5.26 (7~, m), 6.84 (2H~ m); 18.26 (1~
(iv) Ethoxyamine hydrochloride (0.45 g) and ~hen a~ueou~ 1~ sodium hydroxide (18.4 ml) were added to a ~olution o~ 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one (1.2 g; 4.2 mmole) in anhydrous ab~olute ethanol (200 ml~. The mixture was ~tirred at room temperature for a period of 4 hours and then the ethanol was re-moYed by evaporation under reduced pressure using a rotary evaporator. The residue was treated with dichloromethane and the organic phase was washed twice with dilute aqueous hydro-chloric acid and twice with water. The organic phase wa~ dried o~er anhydrous sodium sulfate and the solvent wa~ removed by evaporation under ; reduced pressure to give the product, 2-~I-(ethoxyLmino)propyl7-3-hydroxy-5-meRitylcyclohex-2-en-1-one (1.25 g; 93%), as a pal~ yellow oil~
The product was sharacterized by proton nuclear magnetic resonance and carbon-13 nuclear magnetic . resonance spectroscopy and spectro~copic data i~
recorded in ~able 4, Example 21.
~xame~
Compounds No 1, 2, 3, 4, 5, 6, 8, 9 and 10 t6ee Table 1) were prepared from the appropriate benzaldehyde derivative following essentially the same procedure as that described in Example 1 part~ (i) to ~L28~)7~i~

(iv). Each of the products was characterized by proton nuclear magnetic resonar.ce and/or carbon-13 nuclear magnetic resonance spectroscopy and spectroscopic data is recorded in Table 4, Example 21.
Example 3 3-Benzoyloxy-2-~I-(etho~yimino)propyl7-5-mesityl--cylohex-2-en-1-one (15) a) Aqueous 1~ sodium hydroxide solution (6 ml) was added to a solution of 2-~I- (ethoxyimino)propyl7-3-hydroxy-5-mesitylcyclohex-2-en-1-one (O.42 g; 1.28 mmole) in acetone (50 ml). The mixture was stirred at room temperature for a period of 5 minutes and then benzoyl chloride (O.2 g) was added dropwise.
The mixture was stirred for a further period of 15 minutes and then the solvent was removed by evapora-tion under reduced pressure using a rotary evaporator.
The product was purified by chromatography over silica gel (eluant dichloromethane) to give 3-benzoyloxy-2-~I-(ethoxyimino)propyl7-5-mesitylcyclo-hex-2-en-1-one (0.38 g; 68.6%) as a pale yellow oil.
b) A solution of sodium hydroxide (o.12 g) in water (0.7 ml) was added dropwise, with stirring, to a solution of 2-~I~ (ethoxyimino)propyl7-3-hydroxy-5-mesitylcyclohex-2-en-1-one (0.89 g) in tetrahydro-furan (9.5 ml). Benzoyl chloride (0.42 g) was added dropwise, with stirring and the mixture was stirred at room temperature for a period of 30 minutes. The solvent was removed by evaporation under reduced pressure and the residue was taken up in dichloro-methane and water. The dichloromethane solution was separated, washed twice with water, dried, and the solvent evaporated under reduced pressure. The re-maining oil was triturated with petroleum ether ~LX8~17~8 (b.p. 40-60C) and the solid which for~ed was re-crystallised from isopropanol to give 3-benzoyloxy-2~ ethoxyimino)propyl7-5-mesitylcyclohex-2-en-l-one (0.79 g) as a solid m.p. 94-95.5C.
c) A mixture of 2 ~I-(ethoxyimino)propyl7-3-hydroxy-5-mesitylcyclohex-2-en-1-one (2.4 g), anhydrous methyl ethyl ketone (25 ml) and anhydrous potassium carbonate (1.65 g) was treated dropwise, with stirr-ing, with benzoyl chloride (1.12 g~. The mixture was heated under reflux with stirring for a period of 30 minutes and then filtered. The residue was washed with diethyl ether and the solvent from the combined filtrate and washings was evaporated under reduced pressure. The residue was taken up in ethyl acetate and the solution was washed twice with water, dried, and the solvent was evaporated under reduced pxessure to give a dark brown oil. The oil was purified by chromatography on preparative thin layer chromatography plates (silica gel; eluent hexane/
diethyl ether 75:25) to give 3-benzoyloxy-2~
(ethoxyimino3propyl7-5-mesitylcyclohex-2-en-1-one (1.9 g).
The product was cahracterized by proton nuclear magnetic resonance spectroscopy and spectroscopic data is recorded in ~able 4, Example 21.
Example 4 Compounds No 11, 12, 13, 14, 44, 45, 46, 48, 49, 50, 51, 58, 73, 81, 89, 90, 91, 92, 93, 94 and 95 were prepared from compounds No 5, 5, 3, l, 7, 7, 7, 17, 24, 18, 16, lO, 62~ 60, 7, 7, 7, 7, 7, 7, and 7 and the appropriate acid chloride (ethyl bromoacetate for com-pound no 95) following one of the procedures described in Example 3. Each of the products was characterized 30~6~3 by proton nuclear magnetic resonance spectroscopy and ~pectroscopic data is recorded in Table 4, Example 21.
x~ç~c_5 2~ (Allyloxyim~no)butyl7-3-hy~roxy-5-mesitylcyclohex-2-en-1-one (16) (i) n-Butyryl chloride (2.3 g; 21.7 mmole) and then pyridine (1.7 g: 21.7 mmole) were added to a ~tirred mixture of 3-hydroxy-5-mesitylcyclohex-2-en-1-one ~5.0 g; 21.7 mmole) and dichloro-methane (50 ml) under a nitrogen atmosphere. The mixture was 6tirred at room temperature for a period of two hours and then poured into slightly acidic water. The organic phase was separated and the a~ueous phase was thoroughly extracted with dichloromethane. The combined organic phase an~ extracts were washed with water, dried over anhydrous magne~ium sulfate and the solvent was rem~ved ~y evaporation under reduced pressure using a rotary evaporator. The residue was , 20 dissolved in 1,2-dichloroethane (50 ~1), stannic I chloride (5.7 g; 22 mmole) was added and the mixture was heated under reflux for a period of 8 hours. The mixture was cooled and poured into water and the aqueous mixture was extracted several times with dichloromethane. The combined organic extracts were dried over anhydrous - magnesium ~ulfate and the 001vent was removed by e~aporat$on under reduced pressure using a rotary evaporator. The residue was purified by chromatography over silica gel (eluant ` dichloromethane) to give 2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (2.4 g). Proton ~ucle~r magnetic reson~nce ~pectrum (CDC13: ~ in ppm): 1.01 (3B, t); 1.30-1.60 t2~, ~); 2.23 (3~, lX~3~)7~i~

s); 2.37 (6H~ s); 2.40-3.45 (7H, m); 6.83 (2H, s);
18.24 (lH, s).

(~i) Allyloxyamine hydrochlorid~ (0.72 g) ~nd then aolution of ~odium hydroxide (0.25 g) in water (3 ml) were added to a stirred mixture of 2-butyryl-3-hydroxy-S-mesitylcyclohex~2-en-1-one (1.78.g; 5.9 mmole) and 95% ethanol. The progress of the reaction was monitored using thin layer chromatography on silica gel (eluant dichloro-methane). On completion of the reaction the ethanol was r~moved by evaporation using a rotary evaporator and ~he residue was extracted with dichloromethane. The organic extract was washed wi.th aqueous 5% hydrochloric acid and then with water and dried over anhydrous magnesium sulfate. The solvent was removed b~ evaporation under reduced pressure using a rotary eYaporator to give the product, 2~ (allyloxyimino)butyl7-3-hydroxy-5-mesitylcyclohex-2~en-1-one (1.6 g) as ~n oil.
The product was characterized by proton nuclear ~gn~tic r~on~nce ~pectro~copy and thR ~pectro8cop~c ~at~ is r~coraed ln ~able 4~ ~ample 21 .

Example 6 25 2-~I- (Ethoxyimino)butyl7-3-hydrox~-S-mes~tylcyclohex-2-en-l-one (18) was prepared ~rom 2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (see Example 5 part (i)) and ethoxyamine hydrochloride following essentially the same procedure as that described in Example 1 part (iv). The product was characterized by proton nuclear magnetic resonance spectroscopy and the spectroscopic data is re-ported in Table 4, Example 21.

lX81~768 _ 45 -~xample 7 2~ lAllyloxyimino) propyl7-3-hyaroxy-S-mesitylcyclohex 2-en-1-one (17) was prepared from 3-hydroxy-5-mesityl-2-propio~ylcyclohex-2-en~ ne (see ~xawple 1 parts (i) to (iii)) and allyloxyamine hydrochloride following essentially the same procedure as that described in Example 5 part (ii). The product was characterized by proton nuclear magnetic resonance spectroscopy and the spectroscopic data is reported in Table 4, Example 21.
E ample 8 2~ lPropoxyimuno)pro~y 17- 3-hydroxy-5-mesitylcyclohex-2-en-1-one ~20) (i) A mixture of 3-hydroxy-5-mesitylcyclohex-2-en-1--one (13.0 g, 0.056 mole), propionic anhydride (26 ml) and propionic acid (26 ml) was stirred and heated at 110C until homogeneous. Tri-fluoromethanesulphonic (0.5 ml) was added and the muxture was heated at 110-120C for 1 hour D der an atmosphere of nitrogenO The mixture was poured with stirring into ice-water,neutrali-zed with ~odium bicarbonate and then extracted with diethyl ether. The ether extract gave the crude product as a brown oil which was purified by chromatography over silica gel (eluent di-chloromethane) to give 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one (12.5 g, 77~) as a nearly colourless solid, mp 86-88C.
(ii) 2-~I-(Propoxyimino)propyl7-3-hydroxy-5-mesitylcyclohex-2-en-1-one (20) was prepared from 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one and propoxyamine hydrochloride following ;` ` ~X8~76~
_ 46 -essentially the same procedure as that described in Example 1 part (iv). The product was characterized by proton magnetic resonance spectroscopy and the spectroscopic data is re-ported in Table 4 , Example 21.

ExamEle 9 Compounds No 19, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 52, 53, 54, 55, 56, 57, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 74, 75, 77, 79 and 82 were prepared from the appropriate 5-arylcyclohexane-1,3-dione (see Example 19), the appropriate carboxylic acid anhydride/carboxylic acid mixture and the appropriate hydroxylamine hydrochloride derivative following essentially the same procedure as that described in Example 8. Each of the products was characterized by proton nuclear magnetic resonance spectroscopy and appropriate physical data (melting point for solids and proton chemical shift for liquids is recorded in Table 4, Example 21.
,, Example 10 2~ (Ethoxyimino)propyl7-3-hydrox~5-(pentamethy~
phenyl)cyclohex-2-en-1-one (60) (i) Sodium hydride (0.65 g, 0.027 mole) was added to a stirred solution of 3-hydroxy-5-(penta-methylphenyl)cyclohex-2-en-1-one (6.4 g, 0.024 mole) in dimethylformamide (100 ml) at 60C.
After 15 miDutes propionic anhydride (3.3 g, 0.027 mole) was added and the mixture was heated at 110-120& .for3 hours. It was then poured into water ~300 ml) and extracted with diethyl `30 ether (2 x 100 ml). The ether extracts were dried over anhyarous ~odium sulfate and the solvent was removed by evaporation ~L28~68 under reduced pressure using a rotary evaporator.
The product, a brown oil, was purified by chromatography over silica gel (eluent carbon tetrachloride: chloroform (l:l))to give 3-hydroxy-5-(pentamethylphenyl)-2-propionyl-cyclo-hex-2-en-1-one (4.4 g, 56%) as a nearly colourless ~olid, mp 84C.

(ii) 2-~ Ethoxyimino)propyl7-3-hydroxy-5-(penta-methylphenyl)cyclohex-2-en-1-one (60) was pre-pared from 3-hydroxy-5-pentamethylphenyl-2-propionylcyclohex-2-en-1-one and ethoxyamine hydrochloride following essentially the same procedure as that described in Example 1 part (iv). me product was characterized by proton magnetic resonance spectroscopy and the spectro-scopic data is reported in Table 4, Example 21.

Example 11 Compounds No 71, 76, ~0, 83 and 86 were prepared from the appropriate 5-arylcyclohexane-1,3-dione (see Example 1~, the appropriate carboxylic acid anhydride and the appropriate hydroxylamine hydrochloride derivative following essentially the same procedure as that des-cribed in Example 10. Each of the products was characterized by proton nuclear magnetic resonance spectroscopy and spectroscopic data is recorded in Table 4, Example 21.
'xam~le 12 2-~I-(Ethoxyimino)ethyl7-3-hydroxy-5-(pentamethylphenyl)-cyclohe_-2-en-1-one (70) ~i) A mixture of 3-hydroxy-5-(pentamethylphenyl)-cyclohex-2-en-1-one (3.00 g; see Example 19) acetic - anhydride (10 ml) and acetic acid (10 ml) was ` ` 1.~8~768 _ 48 -stirred and heated under reflux until homogeneous.
~-Toluene sulfonic acid (0.5 g) was added and the mixture was refluxed for a further 2 hours.
After cooling the mixture was poured into water and the solution was extracted with ether. The ether extract was washed several times with water, dried over anhydrous magnesium sulfate and then evaporated to dryness. The product, a brown oil, was purified by column chromatography over silica gel (eluent dichloromethane) to give 3-hydroxy-5-pentamethylphenyl-2-acetyl-cyclohex-2-en-1-one (1.50 g) as a crystalline solid, mp 183~.
(ii) 2-~I-(Ethoxyimino)ethyl7-3-hydroxy-5-(pentamethyl-phenyl)cyclohex-2-en-1-one (70) was prepared from 3-hydroxy-5-pentamethylphenyl-2-acetyl-cyclohex-2-en-1-one and ethoxyamine hydrochloride following essentially the same procedure as that described in Example 1 part (iv). The product was characterized by proton magnetic resonance spectroscopy and the spectroscopic data is re-ported in Table 4, Example 21.
Example 13 2-~I (Ethoxyimino)benzyl7-3-hydroxy-5-(2,5-dimethyl-nhenvl)cyclohex-2-en-l-one ~87) ~I~ A _.
(i~ Sodium hydride (0.53 g, 0.022 mole) was added to a stirred solution of 3-hydroxy-5-(2,5-dimethyl-phenyl)cyclohex-2-en-1-one (4.32 g, 0.020 mole;
see Example 19) in dimethylformamide (60 ml) at 60C. After 30 minutes benzoic anhydride (5.00 g, 0.022 mole~ was added and the mixture was heated at 110-120C for 4 hours. It was then poured into water (300 ml), acidified to pH 3 with hydrochloric acid and extracted with diethyl ether ~2 x 100 ml). The ether extracts were 3076~3 washed with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure.
The crude product, a brown oil, was dissolved in diethyl ether ~200 ml), filtered, shaken with a saturated aqueous cupric acetate solution (300 ml) and then the mixture was evaporated to dryness under reduced pressure. The crude solid was collected, washed successively with hot water, cold water, diethyl ether and-hexane, then air dried to give the copper salt of 2-benzoyl-5-(2,5-dimethylphenyl)-3-hydroxy-cyclohex-2-en-1-one (6.00 g) as a pale green solid mp 182-185C.
The copper salt, suspended in water, was acidified with 3N hydrochloric acid and then extracted into diethyl ether. The ether extract was washed with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure to give 2-benzoyl-5-(2,5-dimethylphenyl)-3-hydroxy-cyclohex-2-en-1-one (4.20 g, 65%) as a pale yellow oil.
Proton nuclear magnetic resonance spectrum (CDC13: ~ in ppm): 2.33 (6H, s~; 2.45-2.90 (4H, m); 3.30-3.70 (lH, m); 6.90-7.15 (3H, brs);
7.30-7.80 (3H, m); 8.00-8.30 (2H, m).
(ii) 2-/I-(Ethoxyimino)benzyl7 3-hydroxy-5-(2,5-dimethylphenyl)cyclohex-2 en-l-one (87) was pre-! pared from 3-hydroxy-5-(2,5-dimethylphenyl)-2-benzoyl-cyclohex-2-en-1-one and ethoxyamine hydrochloride following essentially the same proceduxe as that described in Example 1 part (iv).
~he product was characterized by proton magnetic resonance spectroscopy and the spectroscopic data is reported in Table 4, Example 21.

` : `
31.~8(3768 Example 14 Sodium salt of 2-~1-(ethoxyimino)propyl7-3-hydroxy~5-mesitylcyclohex-2-en-1-one (43) _ A solution of sodium hydroxide (0.45 g) in water (2 ml) was added to a solution of 2-/1-(ethoxyimino)-propyl7-3-hydroxy-5-mesitylcyclohex-2-en-1-one (3.86 g) in acetone (50 ml). The solvent was removed under re-duced pressure using a rotary evaporator to yield the title compound as a yellow solid (3.98 g, 99~), mp 196C (decomp.).
Example 15 Compounds No 47 and 59 (see Table 1) were prepared from the appropriate 2-~1-(alkoxyiminopropyl7-3-hydroxy 5-(substituted phenyl)cyclohex-2-en-1-one derivative and sodium hydroxide following essentially the same pro-cedure as that described in Example 11. The products were characterized by mp data which is recorded in Table 4, Example 21.
Exam~le 16 Copper salt of 2-~I ethoxyimino)butyl7-3-hydroxy-5-(pentamethylphenyl)cy~clohex-2-en-1-one (84) 2-~1-(Ethoxyimino)butyl7-3-hydroxy-5-(penta-methylphenyl)cyclohex-2-en-1-one (400 mg, 1.1 mmole) in diethyl ether (50 ml) was shaken with a saturated aqueous cupric acetate solution (50 ml). The mixture was then evaporated to dryness under reduced pressure. The solid residue was washed successively with hot water, cooled water and diethyl ether, then dried to give the copper salt of 2-~I- (ethoxyimino)butyl7-3-hydroxy-5-(penta-methylphenyl)cyclohex-2-en-1-one (390 mg, 88%) as a pale green solid, mp 210c.

~7 Example 17 Nickel salt of 2-/1-(ethoxyimino)butyl7-3-hydroxy-5-( entameth lDhenvl)cvclohex-2-en-1-one ~85) P Y ~
was prepared following an analogous procedure to that described in Example 16. The product was obtained as a solid and its melting point is recorded in Table 4, Example 21.
Example 18 Tetrabutylammonium salt of 2~ (ethoxyimino)prop~l7-3-hydroxy-5-(2,4,6-trimethylphenyl)c~clohex-2-en-1-one (88) To a solution of 2-/I-(ethoxyimino)propyl7-3-hydroxy-5-(2,4,6-trimethylphenyl)cyclohex-2-en-1-one (329 mg; 10 mmole) in methanol (5 ml) was added a 25~
methanolic solution of tetra-n-butylammonium hydroxide (2.0 ml). The mixture was kept at room temperature for 3 hours and then evaporated to dryness under reduced pressure using a rotary evaporator. m e residue was taken up in dichloromethane (15 ml) and water (15 ml).
The layers were separated and the organic layer washed !' 20 with water (2 x 10 ml), dried over anhydrous sodium ; sulfate and evporated under reduced pressure to afford the tetrabutylammonium salt of 2~ (ethoxyimino)propyl7-3-hydroxy-5-(2,4,6-trimethylphenyl)cyclohex-en-1-one (340 mg), as a pale brown oil. The product was characterized by proton magnetic resonance spectroscopy and the spectroscopic data is reported in Table 4, Example 21.
Example 19 The 5-ar~lcyclohexane-1,3-diones of formula IX
used in the preparation of the compounds of formula I
were prepared from the appropriate benzaldehyde deriva-tive following essentially the same procedure as that described in Example 1 parts (i) and (ii).

~ 52 1~7~8 The majority of the 5-arylcyclohexane-1,3-diones of formula IX were obtained as solids and were characterized by their nuclear magnetic resonance spectra. For convenience, proton nuclear magnetic re-sonance spectroscopic (pmr) data is recorded in Table 2below.

..
OH
(C 3) ~ IX

_ Compound Proton Chemical Shift (CH3)n Appearance~ in ppm (D6-DMSO) _.
2,3-(CH3)2 yellow solid; 2.0-2.8 (lOH,m); 3.4-3.7 mp 209C (lH,m); 5.28 (lH,s); 7.00 (3H,m); 11.2 (l~,brs) 2,4-(CH3)2 yellow solid; 2.0-2.8 (lOH,m); 3.40 (lH
mp 167 C m); 5.25 (lH,s); 6.9-7.3 (3H,m); 11.15 (lH,brs).
2,5-(CH3)2 pale yellow 2.0-3.8 (llH,m); 5.30 solid; (lH,s); 6.8-7.3 (3~,m);
mp 180 C 11.5 (lH,brs) 2,6-(CH3)2 orange solid 2.0-3.8 (ll~,m); 5.28 lH,s); 6.96 ~3H/m); 11.2 (lH,brs) 3,4-(CH3)2 pale yellow 2.0-2.6 (ll~,m); 5.25 solid; (lH,s); 7.00 (3H,m); 11.0 I mp 162C (lH,brs) ~28~)7~

TABLE 2 - continued _ _. .

Compound Proton Chemical Shift (CH3)n Appearance ~ in ppm (D6DMSO) _ 3,5-(CH3)2 yellow solid; 2.0-3.3 (llH,m); 5.25 mp 170 C (lH,s); 6.8-7.0 (3H,m);
11.5 (lH,brs) 2,3,4-(CH3) ¦brown solid 2.0-2.7 (13H,m); 3.0-3.8 (lH,m); 5.28 (lH!s);
6.96 (2H,m); 11.2 (lH,brs) 2,3,5-(CH3)3 yellow solid; 2.20 (6H,s); 2.30 (3H,s);
mp 206C 2.3-3.0 (4H,m); 3.50 (lH, m); 5.25 (lH,s); 6.90 (lH,s); 7.10 (lH,s);
11.0 (lH,brs) 2,3,6-(CH3)3 solid 19 9-3.1 (13H,m); 3.80 (lH,m); 5.28 (lH,s~; 6.91 ~2H,m); 11.3 (lH,brs) 2,4,5-(CH3)3 brown solid; Not recorded mp 112C
2,~,6-(CH3)3 solid; 2.0-4.1 (14H,m); 5.20 (lH, mp 165 C s); 6.80 (2H,s); 11.2 ~lH,brs) 3,4,5-(CH3)3 colorless solid; 2.06 (3H,s); 2120 (6H,s);
mp 206C 2.30-2.85 (4H,m); 3.08 (lH,m); 5.28 (2H,s); 6.91 (2H,s); 11.4 (lH,brs) 2,3,4,5- colorless solid; Not recorded (CH3)4 mp 223 C

TABLE 2 - continued _ Compo~nd Proton Chemical Shift (CH3)n Appearance in ppm (D6DMSO) _ 2,3,4,6- yellow solid; 2.0-2.4 (12H,m); 2.4-3.2 (CH3)4 mp 184C (4H,m) 3.60 (lH,m); 5.25 (lH,s); 6.80 (lH,s); 11.2 (lH,brs) 2,3,5,6- pale yellow 2.20 (12H,s); 2.4-3.2 (CH3)4 solid; (4H,m); 3.60 (lH,m); 5.25 mp 258C (lH,s); 6.80 (lH,s); 11.2 (lH,brs) 2,3,4,5,6- colorless 2.09 (3H,s); 2.11 (6H,s);
(C~3)5 solid; 2.20-2.50 (4H,m); 3.93 mp 235C (lH,m); 5.15 (lH,s);
11.0 (lH,brs~

~'~8~376~

Example 20 -The 2-acyl-5-arylcyclohexane-1,3-diones of formula XIII used in the preparation of the compounds of formula I were prepared from the corresponding 5-arylcyclohexane-1,3-dione of formula IX by acylation us-ing the appropriate acyl derivative following essentially the same procedure as that described in one of Examples 1 part (iii), 5 part (i), 8 part (i), 10 part (i), 12 part (i) and 13 part (i).
The majority of the 2~acyl-5-arylcyclohexane-1,3-diones of formula XIII were obtained as oils and were characterized by their nuclear magnetic resonance spectra. For convenience, proton nuclear magnetic resonance spectroscopic (pmr) data is recorded in Table 3 belo~.

8~76~3 OH

( CH 3 )~'{~ C~o XI I I
~ R3 o _ Compound Proton Chemical Shift (CH3)n ~3 Appearance ~ in ppm (CDC13) 2,3-(CH3)2 C2H5 pale yellow 1.20 (3H,t); 2.25 (6H, solid; 2xs); 2 3-4.0 (7H,m);
mp 100C 7.00 (3H,s); 18020 ~lH,s) 2,4-(CH3)2 C2H5 orange oil 1.10 (3H,t); 2.30 (6H,s) 2.4-3.0 (4H,m); 3.10 (2H,q); 3.40 (lH,m);
7.00 (3H,s);18.10 (lH,s) 2,5-(CH3)2 C2H5 oil 1.20 (3H,t); 2.25 (6H,s);
2.40-3.80 (7H,m); 7.00 (3H,m); 18.20 (lH,s) 2,5-(CH3)2 C6H5 pale yellow 2.33 (6H,s); 2.45-2.90 oil (4H,m); 3.30-3.70 (lH,m);
6.90-7.15 (3H,brs); 7.30-7.80 (3H,m); 8.00-8~30 i ~2H,m) ; 2,6-(CH3)2 C2H5 yellow oil 1.20 (3H,t); 2.40 (6H,s);
2.4-4.0 (7H,m); 7.00 (3H,s); 18.10 (lH,s) __ _ _ ~L2~307~3 TABLE 3 - continued ., ..
Compound Proton Chemical Shift (CH3)n ~3 Appearance ~ in ppm (CDC13) 3,4-(CH3)2 C2H5 pale yellow 1.16 (3H,t); 2.24 (6H,s);
solid; 2.56-3.28 (7H,m); 6.96 mp 100 C (3H,m); 18.24 (lH,s) 3,4-(CH3)2 n~C3H7 pale yellow 1.00 (3H,t); 1.65 (2H,m);
solid; ¦ 2.25 (6H,s); 2.5-3.3 mp 76C (7H,m); 6.98 (3H,m);
18.25 (lH,s) ~
3,5-(CH3)2CzH5 yellow 1.10 (3H,t3; 2.30 (6H,s);
solid; 2.5-3.4 (7H,m); 6~8-7O0 mp 113 C (3H,m); 18.20 (lH,s) 2,3,4- C2H5 brown oil 1.20 (3H,t); 2.20 (9H,m);
(CH3)3 2.50-2.90 (4H,m); 3.10 (2Htq); 3.60 (lH,m);
6.95 (2H,m); 18.10 (lH,s) 2,3,5- C2H5 yellow 1.20 (3H,t); 2.20 (3H,s);
(CH3)3 solid; 2.25 (6H,s); 2.45-3.20 mp 107 C (6H,m); 3.60 (lH,m);
6.80 (lH,s); 6.85 ~lH,s);
18.20 (lH,s) 2,3,6- C2H5 orange 1.20 (3H,t); 2.25 (3H,s);
(CH3)3 oil 2.31 (3H,s); 2.37 (3H,s);
2.5-3.4 (6H,m); 3.82 (lH, m); S.94 (2H,m); 18.18 (lH,s) 2,4,5 C2H5 yellow 1.20 (3H,t); 2.30 (9H,s);
(CH3)3 solid; 2.4-4.0 (7H,m); 7.00 (ZH, _ _ mp 111C s); 18.20 (lH,s) - 58 _ 1~807G~3 TABLE 3 - continued _ Compound Proton Chemical Shift Appearance ~ in ppm (CDC13) (CH3) n R

2,4,6- CH3 colorless 2.24 (3H,s); 2.36 (6H,s);
(CH3) 3 solid; 2.54 (3H,s); 2.65-4.00 (5H ,m); 6.84 (2H ,s);
18.17 (lH,s) 2,4,6- C2H5 solid; 1.60 (3H,t,J=8Hz); 2.24 (CH3~ 3 mp 86-88 C (3H,s); 2.37 (6H,s);
2.64-5.26 (7H,m); 6.84 (2H,m); 18.26 (lH,s) 2,4,6- n-C3H oil 1.01 (3H,t); 1.30-1.60 (CH3) 3 (2H,m); 2.23 (3H,s);
2.37 (6H , s ) ; 2.40 - 3.45 (7H,m); 6.83 (2H,s~;
18.24 (lH,s) 3 ' 4 ' 5~ C2H5 solid; mp 1.14 (3H, t); 2.14 13H, s);
( CH 3) 3 93C 2.28 (6H , s ) ; 2.3- 3.4 (7H,m); 6.79 (2H,s);
18.12 (lH,s) 2,3,4,5-C2H5 pale yellow 1.15 (3H,t); 2.20 (12H, ( CH 3) 4 solid; m); 2.40-2.90 (4H ,m);
mp 97 C 3.10 (2H,q); 3.55 (lEI, m); 6.80 (lH,s); 18.10 (lH,s) 2,3,4,6-C2H5 brown oil 1.20 (3H,t); 2.1-2.4 (CH3) 4 (12H,4xS); 2.4-4.0 (7H, m), 6 ; 90 ( lH , s ); 18.00 ~ i ~8~768 TABLE 3 - continued .
Compound Proton Chemical Shift (CH3) n R Appearance ~ in ppm (CDC13) .. _., l 2,3,4,6- n C3H7 brown oil 1.00 (3H,t); 1.65 ~2H,m) (CH3)4 2.1-2.4 (12H,4xs); 2.4-3.4 (6H,m); 3.80 (lH,m);
6.80 (lH,s); 18.30 (lH, s) 2,3,5,6- C2H5 brown oil 1.20 (3H,t); 2.30 (12H, (CH3) 4 s); 2.4-4.0 (7H,m);
6.80 (lH,s); 18.00 (lH,s 2, 3,4 ,5, 6- CH3 solid; mp Not recorded (CH3) 5 183 C

( CH 3;5 C2H5 84C Not recorded . 2,3,4,5,6- n-C3H7 brown oil 1.00 (3H,t); 1.70 (2H,m) (CH3) 5 2.18 (9H,s); 2.25 (6H,s) 2.25 (6H,s); 2.25-3.40 (6H,m); 3 . 90 ( lH ,m);
_ 18.10 (lH,s) ~ 8~76~3 Example2 The majority of the compounds of the inventio~
were obtained as oil~ and were characterized by, and can be identified by their nuclear magnetic resonance spectra. For conve~ience proton nuclear magnetic resonance spectroscopic (pmr) data is recorded in Table 4a below and carbon-13 nuclear magnetic resonance spectxoscopic data i6 recorded in Table 4b below.
TABLE ~ Part (a) No Appearanc2 Prot~n Chemical Sh~ft _ _ _ , . __ 1 Solid; 1.04-1.39 (6H,m); 2.28 (3H,s);
mp 70C 2.32 (3~1,s~; 2.63-4.01 (9~1,~);
7.07 (3H,m); 15"03 (lH,br.s).
2 ~ale yellow 1 . 10-1 . 39 ( 6H ,m); 2 . 2 8 ( 3H , 6);
oil 2.31 (3H,~; 2.40-2.70 ~4H,m);
2.97 (2H,q,J=8Hz); 3.52 ~lH,m);
4 .10 ~ 2H ,q, J=8Hz~; 7 . 00-7 .15 (3H,m); 15.0 (lH,br.6).
3 Pale yellow 1.11-1.40 (6H,m); 2.31 (6H,s);
oil 2.64-3.02 (6H,m); 3.53 (lH,m);
~,.12 ~2H,q,J=8Hz); 7.00-7.23 (3H,m); 15.03 (lH,br,~).
Pale yellow 1.12-1.40 (6E~,m) 5 2.41 (6H,s);

~L2~ 76~3 TABLE 4 Part (a) continued _ _ ~ r Com- Proton Chemical Shift PNoUnd Appearance ~ in ppm (CDC13) _ _ _ _ 4 oil 2.62-3.14 (6~,m); 3.85 (lH,m);
. 4.12 (2H,g,J=8Hz); 7.01 (3H,s);
15.03 (lH,br.s)~
Pale yellow 1.10-1.37 (6H,m~; 2.22 (6H,s);
oil 2,60-2.92 ~7H,m); 4.07 (2H/q, J=8Hz); 6.97-7.04 (3H,m);
14.70 (lH,br.~).
6 Pale yellow 1.08-1.39 (6H,m); 2.30 (6~, 5);
oil 2.65-3.00 (7H,m); 4.10 (2H,q, J=8Hz); 6.85 (3H,s); 15.0 (lH,s).
7 Pale yello,w 1.13-1.48 l6H,m); 2.23 (3B,s);
oil 2.37 ~6H,s); 2.60-~.23 ~g~,m);
6.83 l2H,8~; 14.99 (lH,s).
8 Pale yellow 1.07-1.40 (SH,~ ; 2.21 (6H,s);
oil 2.27 (3H,s); 2.36 3.07 (6~,m);
3.42 (lH,m); 4.10 (2H,q,J=8Hz);
6.95-7.23 (ZH,m); 15.0 (l~,br.s)~
9 Pale yellow 1.07-1.41 (6H,~ 2.23 (6H,s);
oil 2.27 (6H,s); 2.41-3.16 (6~,m);
4.00-4.12 (3H,m); 6.91 (l~,s);
15.0 tlH~br.~).
Pale yellow 1,07-1.41 (6~,m); 2.16 (3~,8);
oil 2,24 t3H,8); 2.32 (3H,s~; 2.35 (3H,~)~ 2.40-3.35 (6H,m); 3.41-4.07 (3H,~); 6.86 (lH,s); 15.0 (l~br.s).
11 Pale yellow 0.92-1.74 (6H,m); 2.22 (6H,s);
_ oil 2.24-3.15 (7H,n~; 3 99 (lH,q, .

7~i~

TP~LE 4 Part ( a) continued _ _ , .

Com- Proton Chemical Shi f t pound A}?pearance ~ in ppm (CDC13) _ _ J=8Hz3; 7.04-8.10 (8H,m).
12 Pale ye ll~w 0 . 90 ~1 . 34 ( 6H , m); 2 . 16 ( 3H , s);
oil 2.22 S6~,s); 2.24-3.15 (7H,m);
4.13 (2EI,q,J=8Hz); 7.00-7.25 ( 3~1 ,m) .
13 Pale yellow 1.10-1.39 t6H,m); 2.31 (6H,~);
oil 2.64-3.02 (6H,m); 3.53 (lH,m);
4.12 (2H,q,J=8Hz); 7.00-7.23 (3~,m); 7.38-8.10 ~5H~m).
14 Pale yellow 1.04-1.39 (6H,m); 2.28 (3E~,s);
oil 2.32 ~3H,~;); 2.63-4.01 (9H,m);
7.07 ~3El,m); 7O38-8~08 (5H,m).
Pale yellow 1.13-1.4B (6El,m); 2.24 (3H,s);
oil 2.42 (6El,s); 2.42-3.90 (9H,m~;
6.85 ~2~ ); 7.24-8.08 (sH,m).
16 Pale yellow 1.05 (3E~,t); 1.30-1.60 (2H~,~);
oil 2.23 (3H,s); 2.37 (6H,~); 2.40-3.90 (7~,m); 4.61 (2}~,m); 5.34 (2~,m); 5.80 (lH,m); 6.80 (2H,8) S
14.70 (1~
1~ Pale yellow 1.10 (3~,t)~ 2.21 ~3~,~); 2.37 , oil (6H,s) ; 2~5-3.95 ~8~,m); 4.52 (2~,~); 5.34 (2H,m); 5.80 (lff,m);
6.8~ (2~,~); 14.7 (1~,~).
18 Pale yellow 1.05 l3H,t); 1.32 (3H,t); 1.66 oil (2H,m); 2.23 (3H,~) 2.37 (6H,~);
2.4-3.95 (7H,m); 4.15 (2H,q);
L 6.83 (2H,~)7 15.13 (1~
. _ , ~LZ8C~68 TA~LE 4 Part (a) continued .
_ Com- Proton Chemical Shif t pound Appearance ~ in ppm (CDC13) _ 19 pale yellow 1.32 (3H,t); 2.23 (3H,s); 2.37 oil (6H,s) î 2.41 (3H,s); 2.4--4.0 (5H,m); 4.12 ~2H,q); 6.83 (2H,s);
14.7 (lH,s) .
solid; 0.99 (3H,t); 1.21 (3H,t); - 1.69 mp 114C (2H,m); 2.23 (3H,s); 2.37 (6H,s);
2.3-3.9 (7H,m); 4.01 (2H,t);
6.83 (2H,s); 14.99 (lH,s).
21 solid; 0.95 (3H,t); 1.20 (3H,t); 1.2-1.8 mp 70-72C (4H,m); 2.24 (3H,s); 2.37 (6H,s);
2.3-3.9 (5H,m); 2.95 (2H,q); 4.û6 (2H,t); 6.84 (2H,s); 15.05 (lH,s) .
22 solid; 1.19 (3H, t); 1.77 (3H,d,J=6Hz);
mp 89-91C 2.24 (3H,s); 2.37 (6H,s); 2.3--3.9 (5H,m); 2.95 (2H,q); 4.47 (2H,d, J=Hz); 5.6-5.9 (2H,m); 6.83 (2H,s), 14.9 (lH,s).
23 solid; 1.19 (3H,t); 2.24 (3H,s), 2.37 mp 69-71C (6H,s); 2.3-3.9 (5H,m); 2.94 (2H,q); 4.12 (2H,t); 5.0-5.3 (2H, m); 5.6-6.0 (lH,m); 6.84 (2H,s);
14.8 (lH,brs).
24 pale yellow 1.19 t 3H, t); 2.24 ~ 3H, s); 2.37 oil (6H,s); 2.4-3.9 (8H,m); 4.64 (2H, d,J=2.4Hz); 6.84 (2H,s); 13.90 (lH,s) .
pale yellow 1.20 (3H,t); 2.24 (3H,s); 2.37 (6H
oil 6); 2.4-3.9 (5H,m); 2.95 (2H,q);

o~8 _ 64 -TABLE 4 Part (a) continued _ Com- Proton Chemical Shift pound Appearance ~ in ppm (CDC13) .... _ .
pale yellow 4,10-4.20 (lH,m); 4.36-4.48 (2.~, oil m); 4.89-4.98 (lH,r); 6.84 (2H, s); 14.06 (lH,brs).
26 pale yellow 1.22 (3H,t); 2.24 (3H,s); 2.38 oil (6H,s); 2.4-3.9 (5M,m); 2.99 (2H,q); 4.60 (2H,s); 5.47 (2H,s);
6.84 (2~1,s); 14.5 (lH,brs).
27 pale yellow 1.19 (3H,t); 2.23 (3H,s); 2.35 oil (6H,s); 2.4-3.9 (5H,m), 2.90 (2H, q); 5.06 (2H,s); 6.82 (2HIm); 7.3 (5H,m); 14.3 (lH,s).
28 pale yellow 1.18 (3H,t); 2.24 (3H,s); 2.36 oil (6H,s); 2.4-3.9 (7H,m); 5.03 (2H, s); 6.83 (2H,s); 7.33 (4H,s);
14.16 (l~,s).
29 pale yellow 1.18 (3H,t); 2.24 (3H,s); 2.36 oil (6H,s); 2.4-3.9 (7~,m); 5.02 (2H, s); 6.83 (2H,s); 7.37 (4H,dofd);
14.5 (lH,s) .
solid; 1.18 (3H,t); 2.24 (3H,s); 2.36 mp 68-70C (6H,s); 2.3-3.9 (7H,m); 5.03 (2H, s); 6.83 (2H,s); 7.0-7.4 (4H,m);
14.2~ (lH,s).
31 pale yellow 1.18 (3H,t); 2.22 (3H,s); 2.34 oil (9H,s); 2.3-3.9 (7H,m); 5.01 (2H, s); 6.82 (2H,s); 7.21 (4H,dofd);
l 14.45 (lH,s) .
32 I solid; 1.21 (3H,t); 2.24 (3H,s); 2.35 I mp ~50 C ¦ (6H,s); 2.4-3.9 (7H,m); 5.18 I _ /

~ ~.2~q6~
_ 65 -TABLE 4 Part la) continued Com- Proton Chemical Shift pound Appearance ~ in ppm (CDC13) . .
32 solid; (2H,s); 6.83 (2H,s); 7.88 (gH, mp <50C dofd); 13.74 (lH,s).
33 pale yellow 1.20 (3H, t); 2.22 (3E~, s); 2.34 oil (6H,s); 2.4-3.9 (7H,m); 5.02 (2H, s); 6.81 (2H,s); 7.2-7.34 (4H,m);
14.03 (lH,s) .
34 solid; 1.20 (3H,t); 2.23 (3H,s); 2.35 mp <50C (6H,s); 2.4-3.9 (7H,m); 5.15 (2H, s); 6.83 (2H,s); 7.19-7.40 (3H,m);
14.0 (lH,s).
solid; 0.9-1.2 (6H ,m); 1. 3-1.8 (6H ,m);
mp 7hC 2.25 (3H,s); 2.38 (6H,s); 2.4~3.9 (7H,m); 4.07 (2H,t); 6.84 (2H,s);
14 (lH,brs).
36 solid; 1.00 (3~,t); 1.5-1.8 (5H,m); 2.24 mp 68-70C (3H,s); 2.37 (6H,s); 2.4-3.9 (7H, m); 4.46 (2H,d,J=6Hz); 5.4-6.0 (2H,m); 6.84 (2H,s); 14 (lH,brs).
37 solid; 1.00 (3H, t); 1.3-1.6 (2H ,m), 2.22 mp 70-71 C (3E~,s); 2.36 (6H,s); 2,4-3.9 (7H ,m); 4.10 (2H, t); 5.0-5.3 (2H, m); 5.6-6.0 (lH,m); 6.82 (2H,s);
14.6 (lH,s) .
38 pale yellow 0,97 (3H,t); 1 6 (2H,m); 2.24 (3H, oil s); 2.37 (6H,s); 2.4-3.7 (8H,m);
4.65 (2H,d,J=2,4Hz); 6.84 (2H,s);
14.1 (lH,s).

~807~3 TABLE 4 Part (a) continued Com- Appearance ~ in ppm (CDC13) :
39 pale yellow 1.00 (3H,t); 1.3-1.6 (2H,m); 2.24 oii (3H,s); 2.38 (6H,s); 2.A-3.9 (7H, m); 4.1-4.2 (lH,m); 4.36-4.51 (2H, m); 4.89-4.98 (lH,m); 6.84 (2H,s);
14 (lH,brs).
solid; 1.00 (3H,t); 1.3-1.6 (2H,m);
mp 92-94C 2~24 (3H,s); 2.37 (6H,s); 2.4-3.9 (7H,m); 4.59 (2H,s); 5.48 (2H,s);
6.84 (2H,s); 14 (lH,brs).
41 pale yellow 0.99 (3H,t); 1.4-1.7 (2H,m); 2.21 oil (3H,s); 2.34 (6H,s); 2.4-3.9 (7H, m); 5.00 (2H,s); 6.81 (2H,s); 7.30 (4H,s); 14.23 ~lH,s).
42 pale yellow 0.99 (3H,t); 1.4-1.7 (2H,m); 2.23 oil (3H,s); 2.35 (6H,s); 2.4-3,9 (7H, m); 5.00 (2H,s); 6.83 (2H,s); 7.36 (4H,dofd); 14 (lH,brs)~
43 pale yellow Not recorded solid, mp 196C
(decomp.) 44 pale brown 0.90-1.20 (6H,m); 2.10 (3H,s);
solid; 2.30 (6H,s); 2.2-3.7 (6H,m); 3.99 mp 45-50C (3H,m); 6.85 (2H,s); 8.10 (4H, dod~.
4 5 pale brown 1.0-1.2 (6H,m); 2.10 (3H,s); 2.30 solid, (6H,s); 2.3-3.6 (6H,m); 3.99 (3H, Ij mp ~50C m); 6.80 (2H,s); 8.20 (4H,m).
I__ TABLE 4 Part (a) continued .
_ Com- Proton Chemical Shift pound Appearance ~ in ppm (CDC13) 46 pale brown 1.0-1.3 (6H,m); 2.25 (3H,s); 2.45 solid; (6H,s); 2.5-4.2 (9H,m); 6.80 mp 83C (2H,s); 9.20 (3H,m).
47 yellow solid; Not recorded mp 200C
(decomp.) 48 pale yellow 1.04 (3H,t); 2.24 (3H,s); 2.42 oil (6H,s); 2.4-3.7 (5H,m); 4.46 (2H, d,J=6Hz); 5.12 (2H,m); 5.64 (lH, m), 6.85 (2H,s); 7.2-8.1 (5H,m).
49 Pale yellow 1.04 (3H,t); 2.22 (3H,s); 2.40 oil (6H,s~; 2.4 3.9 (7H,m); 4.55 (2H, d,J=2.4Hz); 6.82 (2H,s); 7.4-8.1 (5H,m).
Pale orange 0.83-1.10 (6H,m); 1.53 (2H,m);
oil 2.23 (3H,s); 2.42 (6H,s); 2.4-3.7 (7H,m); 4.00 (2H,q,J=8Hz); 6.84 (2H,s); 7.28-8.08 (5H,m).
51 orange oil 0.92 (3H,t); 1.53 (2H,m), 2.23 (3H,s); 2.42 (6H,s); 2.5-4.4 (7H, m), 4.46(2H,d) 4.96 (2H,dofd);
5.77 tlH,m); 6.84 (2H,s); 7.2-8.1 t5H,m) .
52 pale hrown 1.10 (3H,~); 1.25 (3~,t); 2.20 oil (3H,s); 2.26 (6H,s); 2.4-3.7 (5H,m); 2.96 (2H,q); 4.11 (2H,q);
_ 6.99 (2H,s); 14.98 (lH,brs).

~3()768 -- 6~ --TABLE 4 Part _) continued Com- Proton Chemical Shi ft pound A~?pearance ~ in ppm (CDC13) _ 53 yellow oil 1.10-1.40 (6H,2xt); 2.20 (3H,s);
2.26 (6H,s); 2.86-3.01 (6H,m);
3.56 (lH,m); 4.11 (2H,q); 6.89 (2H,s); 15.02 (lH,s) .
54 pale yellow 1.17 (3H,t); 1.34 (3E~,t); 2.15 oil (3H,s); 2.28 (6H,s); 2.5-3.4 (7H,m); 4.04 (2H,q); 6.87 l2H,s);
14. 95 (lH ,s) .
ye llow oi l 0.92 -1.40 (6H , m), 1.62 (2H ,m);
2.16 (3H,s); 2.24 (3H,s); 2.32 (3H,s); 2.34 (3H,s); 2.6-3.0 (6H, m); 3.74-4.23 (3H,m) 6.85 (lH,s);
- 15.1 (lH,s) .
56 palebrown 1.19 (3H,t); 2.14 ~3H,s); 2.24 oil ~3H,s); 2.32 (3H,s~; 2.34 (3H,s);
274-3.14 (6H,m); 3.80 (lH,m);
4.53 (2H, d, J=6~ z); 4.35 (2H ,m);
5.90 (lH,m); 6.83 (lH,s); 1d,.5 (lH,brs) .
57 yellow oil 0.97 (3H,t); 1.62 (2H,m); 2.13 (3H,s); 2.22 (3H,s); 2.29 (3H,s);
2.32 (3H,s); 2.60-3.02 (6H,m);
3.80 (lH,m); 4.51 (2H,d,J=6Hz);
5.24 (2H,m); 5.80 (lH,m); 6.83 (lH,s); 14.65 (lH,s) .
58 palebrown 0.99 (3H,t); 1.17 (3H,t); 2.17 oil (3H,s); 2.25 (3rl,s); 2.39 (3H,s) 2.49 ~3H,s); 2.4-3.5 (6H,m);
.

~ 8~8 TABLE 4 Part (a) continued Com- Proton Chemical Shift pound Appearance ~ in ppm (CDC13) 58 pale brown 3.5-4.13 (3H,m); 6.87 (lH,s);
oil 7.25-7.56 (3H,m); 8.03-8.09 (2H,ml 59 yellow solid Not recorded mp 250C
~decomp.) pale yellow 1.00-1.30 (6H,m); 2.10 (9H,s);
solid, 2.15 (6H,s); 2.2-3.3 (6H,m); 3.6-mp 121C 4.15 (3H,m); 14.80 (lH,s).
61 pale yellow 1.21 (3H,t), 2.14 (9H,s); 2.32 solid; (6H,s); 2.43-3.86 (6H,m); 4.00 mp <50C (lH,m); 4.50 (2H,d,J=7Hz~; 5.37 (2H,m); 5.89 ~lH,m); 14.53 (lH,s).
62 pale brown 1.00-1.32 (6H,2xt); 1.62 (2H,m);
solid; 2.22 (9H,s); 2.32 (6H,s); 2.4-3.1 mp 116C (6H,m); 3.99-4.23 (3H,m); 15.06 (lH,s).
63 pale brown 1.00 (3H,t); 1.63 (2H,m); 2.21 oil (9H,s); 2.31 ~6El,s); 2.49-3.00 (6H,m); 4.00 (~I,m); 4.52 (2H,d, J=7Hz); 5.36 (2H,m); 5.88 (lH,m);
14.60 (lH,s).
64 yellow oil 1.04-1.40 (6H,2xt); 2.19-2.27 (12H,m); 2.67 (4H,m); 2.97 (2H,q);
3.59 (lH,m); 4.11 (2EI,q); 6.87 (lEI,~); 15.0 ~lH,brs).
pale yellow 0.98 (3H,t); 1.18 (3H,t); 1.68 oil (2H,m); 2.24 (6H,s); 2.5-3.4 (7H,m); 4.00 (2H,t); 6.9-7.1 (3H,m); 14 (lH,brs).
.

- 70 - ~Z~07~8 TABLE 4 Part ta) continued Com- Proton Ch~mical Shift No Appearance ~ in ppm (CDC13) 66 pale yellow 1.17 (3H,t); 2.25 (6H,s); 2.5-3.4 oil (7H,m); 4.54 (2H,d,J=6.4Hz); 5.35 (2H,m); ~.90 (lH,m); 6.9-7.2 (3H, m); 14.6 (lH,s).
67 pale yellow 0.98 (3H,t); 1.32 (3H,~); l.S
oil (2H,m); 2.25 (6H,s); 2.5-3.4 (7H, m); 4.10 (2H,q); 7.00-7,25 (3H,m);
15.1 (lH,brs).
68 pale yellow 0.98 (6H,t); 1.63 (4H,m); 2.24 oil (6H,s); 2.5-3.4 (7H,m); 4.01 (2M,q); 6.95-7.25 ~3H,m); 14 (lH, brs).
69 pale yellow 0.98 ~3H,t); 1.63 (2H,m); 2.25 oil ~6H,s); 2.5-3.4 (7H,m); 4.52 (2H,d,J=6.4Hz); 5.25-5.44 (2H,m);
5.79-6.21 (lH,m); 6.90-7.25 (3H, m); 14.6 (lH,s).
pale brown 1.32 (3H,t); 2.13-3.45 (23H,m);
solid; 4.13 (2H,q); 14.68 (lH,brs) mp 183C
71 pale yellow 1~12-1.40 (6H,m); 2.22 (3H,s);
oil 2.30 (3H,s); 2.38 (3~,s); 2.63-2.99 ~6H,m); 4.00-4.24 (3H,m);
5.93 (2H,m); 14.99 (lH,brs) 72 solid; Not recorded mp >250C

-\ ~

~ - 71 - ~28~76~
TABLE 4 Part (a) continued ... I _ _ _ Com- Proton Chemical Shift pound Appearance ~ in ppm (CDC13) . _ _ _ 73 pale yellow 0.92 (3H,t); 1.10 (3H,t); 1.48 oil (2H,m); 2.23-3.76 (22H,m); 4.00 (2H,q); 7.45-8.09 (5H,m) 74 pale yellow 0.99 (3H,t); 1.60 (2H,m); 2.10-oil 4.90 (23H,m); 6.85 (lH,s); 13.95 (lH,brs) pale brown 0.99 (3H,t); 1.63 (2H,m); 2.22-solid; 4.94 (26H,m); 14.00 (lH,brs) mp 132C
76 oil 1.21 (3H,t); 2.22-4.89 ~26H,m);
13.94 (lH,brs) 77 solid; Not recorded mp 96C
78 solid; mp Not recorded >250C
79 oil 0.99 (6~,2xt); 1.69 (4H,m); 2.22-3.38 (22H,m); 4.02 (2H,t); 15.15 (lH,brs) oil 1.19 (3H,t); 2.22-2.83 (22H,m);
3.90 (3H,s); 14.71 (lH,brs) 81 oil 1.09 (6H,2xt); 2.23-3.74 (22H,m);
4.02 (2H,q); 7.45-8.08 (SH,m) 82 oil 1.01 (3H,t); 1.66 (2H,m); 2.23-4.06 (22~,m); 4.60 (2H,s); 5.48 (2H,s);
14.0 (~I,brs) 83 oil 1.20 (3H,t); 1.77 ~3H,d); 2.23-4.20 (22H,m); 4.47 (2H,d); 5.74 _ _ _ (2H,m); 14.0 (lH,brs) 72 ~8~3768 .

TABLE 4 Part (a) continued .
Com- Proton Chemical Shift pound Appearance ~ in ppm (CDC13) 84 pale green Not recorded solid; mp mp 210C
pale brown Not recorded solid;
mp 240C
86 oil 1.22 (3H,t); 2.22-4.22 (25H,m);
5.12 (2H,s); 14.04 (lH,s) 87 pale brown 1.22 (3H,t); 2.31 (3H,s); 2.35-oil 3.70 (5H,m); 3.95-4.45 (2H,m);
6.90-7.15 (3H,brs); 7.30-7.80 (3H, m); 8.00-8.30 (2H,m) 88 pale brown 0.71-1.82 (34H,m~; 2.22 (3H,s);
oil 2.36 (6H,s); 1.99-2.70 (4H,m);
2.76-4.27 (llH,m); 4.07 (2H,q);
6.78 12H,s) 89 oil 0.8-1.4 (6H,mj; 2.26 (3H,s); 2.45 t9H,s); 2.45-4.0 (9H,m); 6.92 (2H, s); 7.34 (2H,d); 8.0 ~2H,d) oil 0.7-1.4 (6H,m); 2.25 (12H,s); 2.37 (6H,s); 2.37-4.0 (9H,m), 6.85 (4H, ~) 91 oil 0.8-1.3 ~6H,m); 2.24 (3H,s); 2.42 (6H,s); 2.42~4.0 (12H,m+s); 6.85 (2H,8); 6.9 (2H,d); 7.95 (2H,d) I

TABLE 4 Part (a? continued _ , _ . .

rotor Chemi 1 Shift 92 oil 0.8-1.3 (6H,m); 2.24 (3B,s); 2.44 (6H,s); 2.45-4.2 (9H,m); 6.86 (2H, s); 7.96 (2El,d); 7.44 (2H,d) 93oil 1.01 (3H,t); 1.27 (3H,t); 2016 (3H, 8); 2.20 (3H,s); 2.38 (6H,s); 2.4-4.3 (9H,m); 6.84 (2H,s) 94oil 0.99 (3H,t); 1.23 (12H,s+t); 2.24 (3H,s); 2.40 (6H,s); 2.45-4.3 (9H,m); 6.85 (2H,s) 95s~lid; mp 0.9-1.4 (9H,m); 2.24 (3H,s); 2,38 138-142 C (6H,s); 2.4-4.2 ~llH,m); 4.62 _ _ (2H,s) 6.90 (2H,s) ~28~)768 TABLE 4 ~art ~b) _ ~ ~_ _ _ Com-No Carbon-13 Chemu~al Shi~t ~ in ppm (CDC13) _ 1 11.26 Il~); 14.14 (lC); 1~.68 (lC); 20.37 (2~);
33.91 (lC); 39-45 (2C); 70.26 (lC); 107.10 (lC); 122.79 llC); 125085 (lC); 128.50 (lC);
134.03 (1~); 137.22 (lC); 140.20 (lC);
16~.53 (lC); 184-195 (2C).
2 11.22 (lC?; 14.01 (lC3; 19.07 tlC); 20.69 (lC);
20.86 (lC); 33.32 (lC); 39-45 (2C); 70.~1 (lC);
107.05 ~lC); 124.82 (lC); 126.~9 (lC); 131.48 (lC); 135022 (lC); 136.14 (lC); 137.39 (1~);
166.53 (lC); lR4-195 (2C).
3 11.32 (lC): 14019 (1~: 18.~5 (lC): 21.07 ~lC):
21.18 (lC): 33.75 (1~): 39-45 (2C): 7~.3~ (lC):
107.21 (1~: 125.85 (1~): 127,47 (lC~: 130.78 (lC); 132.35 (lC); 135.02 (lC); 140.31 ~lC);
1~6.5g ~lC~; 18~-195 (2C).
4 11.27 (lC); 14.14 (lC); 21~13 (lC); 21.94 (2C);
33.75 ~lC); 39-45 (~C); 70.37 (lC); 107.21 ~lC) 126.77 (lC); 129~91 (2C); 136.36 (2~; 137.49 (lC); 166.75 (lC); 184-195 ~2C).
5 11.32 (lC); 14.25 (lC); 19.34 (lC); 19.88 (lC);
21.02 ~lC); 37.38 (lC); 39-~5 (2C); 70.26 (lC);
107.4~ (lC); 123.90 (lC)~ 128.07 (lC); 130.02 (lC); 135.17 (lC~; 136.84 ~lC); 140.15 (lC);
166.34 (lC); 184-195 (2C).
6 11.21 (lC); 14.0g (lC); 20.86 ~2C); 21.29 (lC);
37.54 (lC); 39-45 ~2C) ~ 70.26 (lC); 107.27 (lC) 124.33 (2C); 128.56 ~lC); 138~20 (2C); 142.42 (lC); 166.48 (lC); 184-195 (2C).
_ . _ _ _ _ . _ _ _ 75 ~ 076~

Example 22 This non-limiting Example illustrates the pre-paration of formulations of the compounds of the in-vention.
a) Emulsifiable Concentrate _ Compound No 7 was dissolved in ~oluene containing 7% v/v "Teric" N13 and 3% v/v "Kemmat" SC15B to give an emulsifiable concentrate which may be diluted with water to the required concentration to give an aqueous emulsion which may be applied by spraying.
("Teric" is a Trade Mark and "Teric" N13, is a product o~ ethoxylation of nonylphenol; "Kemmat"
is a Trade Mark and ~Kemmat" SC15B is a formulation of calcium dodecylbenzenesulfonate.) b) ~queous Suspension Compound No 7 (5 parts by weight) and "Dyapol" PT
(1 part by weight) was added to an aqueous solution (94 parts by weight) of "Teric" N8 and the mixture was ball milled to produce a stable aqueous ~uspen-sion which may be diluted with water to the required concentration to give an aqueous suspension which may be applied by spraying. ("Dyapol" is a Trade Mark and "Dyapol~ PT is an anionic suspending agent;
NTeric" N8 is a product of ethoxylation of nonyl-phenol~) c) Emulsifiable Concentrate Compound No 7 (10 parts by weight), NTeric" N13 (5 parts by weight) and "Kemm~t~ SC15B (5 parts by weight) were dissolved in "Solvesso" 150 (80 parts by weight) to give an emulsifiable concentrate which may be diluted with water to the required con-- 76 _ ~8~76~
centration to give an aqueous emulsion which may be applied by spraying. ("Solvesso" is a Trade Mark and "Solvesso" 150 is a high boiling point aromatic petroleum fraction.) d) Dispersible Powder Compound No 7 (10 parts by weight), "Matexil" DA/AC
(3 parts by weight), "Aerosol" OT/B (1 part by weight) and china clay 298 ~86 parts by weight) were blended and then milled to give a powder composition having a particle size below 50 microns. ("Matexil"
is a Trade Mark and "Matexil" DA/AC is the disodium salt of a naphthalenesulfonic acid/formaldehyde con-densate; "Aerosol" is a Trade Mark and "Aerosol"
OT/B is a formulation of the dioctyl ester of sodium sulfosuccinic acid.~
e) High Strength Concentrato . Compound No 7 (99 parts by weight), silica aerogel (0.5 parts by weight) and synthetic amorphou~ silica (0.5 parts by weight) were blended and yround in a hammer-mill to produce a powder having a particle size less than 200 microns~
f) Dusting Powder Compound No 7 (10 parts by weight), attapulgite (10 parts by weight) and pyrophyllite (80 parts by weight) were thoroughly blended and then ground in a hammer-mill to produce a powder of particle size less than 200 microns.

Emulsifiable concentrates andJor suspensions of the compounds of the invention were prepared essentially as described in part a), b) or c) above and then diluted with water, optionally containing a surface active agent and/or oil, to give aqueous compositions of 8(~1768 the required concentration which were used, as described ir, Examples 23 and 24, in the evaluation of the pre-emergence and post-emergence herbicidal activity of the compounds.

~Z~30768 Example 23 The pre-em~rgent herbicidal acti~ity of the com-pounds o~ the invention ~osmulated as described in Example 2~ was assessed by the following procedure:
S The seeds of the test species were sown in rows 2 cm deep in soil contained i~ seed boxes. The m~no-cotyledonous plants and the dicotyledonous plants were ~own in separate boxes and a~ter sowing the two boxes were sprayed with the reguired guantity of a composition of the invention. Two duplicate seed boxes were pre-pared in the same manner but were not sprayed with a composition of the invention and were used for com-parison purposes~ All the boxes were placed in a glass-house, lightly watered with an overhead spray to initiate germination and then sub-irrigated as required for optimum plant growth. After three weeks the boxes were removed from the glasshouse and the effects of the treatment was vi~ually assessed. The results are pre-ented in Table ~ where the damage to plants is rated .~ 20 on ~ ~cale of ~rom 0 to 5 where O repre~ents from 0 to 104 damage, 1 represents from 11 to 30~ damage, 2 represents from 31 to 60% damage, 3 rcpresents ~rom 61 to 80% damage, 4 xepresents from 81 to 99~ damage and 5 represents 100% kill. A dash (-) means that no experi-ment wa~ carried out.
m e names of the test plants are as follows:
Wh Wheat Ot Wild Oa~s Rg ~yegrass Jm ' Japanese millet p Peas Ip Ipomea Ms Mustard Sf Sunflower 1;~ )7~3 PRE-EMERGENCE HERBICIDAL ACTIVITY
. . ~
TEST PLANT
Com~ APPLI CATI ON _ pound Rate (kg/ha) _ Ot Rg Jm _ Ip _ S

9 2.0 3 5 5 5 0 0 0 0 9 0.5 0 5 5 5 0 0 0 0 2.0 1 5 5 5 0 0 . 0 0 0.5 0 5 5 5 0 ~ 0 0 16 2.0 4 5 5 5 0 0 0 0 16 0.5 0 5 5 5 0 0 0` 0 18 2 .0 2 5 5 5 0 0 n o 18 0.5 0 5 5 4 0 0 0 0 19 2.0 3 5 5 5 0 0 0 0 19 0.5 0 3 5 5 0 0 0 0 24 2.0 0 5 5 5 0 0 0 0 24 0.5 0 0 5 5 ~ 0 0 0 1.0 2 5 5 5 0 0 0 0 0.25 1 1 5 5 0 0 0 0 26 1.0 1 4 S 5 0 0 0 0 26 0 . 25 0 0 5 5 0 0 0 0 38 2.0 0 2 5 4 0 0 0 0 38 0.5 0 3 5 4 0 0 0 0 47 2.0 4 5 5 5 0 0 0 0 47 0.5 0 0 5 4 0 0 0 0 2.0 4 5 5 5 0 0 0 0 0.5 0 4 5 4 0 0 0 0 52 1.0 0 1 5 5 o !o 52 ' 0.25 0 0 4 ' 1 :~ `
~8~ 8 TABLE 5 Continued PRE-EMERGENCE HERBICIDAL ACTIVITY

TEST PLANT
Com- APPLI CATION
pNund Rate (kg/ha) _ _ _ _ o _ _ Ot Rg Jm _ Ip Ms S f 54 2.0 3 4 5 5 0 0 0 0 54 0.5 0 0 5 5 0 0 0 0 56 1.0 0 3 5 5 0 0 0 0 56 0 .25 0 2 5 5 0 0 0 0 59 1.0 4 5 5 5 0 0 0 0 59 0.~5 2 5 5 5 0 0 0 0 61 1.0 0 2 4 5 0 0 0 0 ii 61 . 0.25 0 0 5 4 0 0 0 0 .~ 67 1.0 0 5 5 1 0 0 0 0 ~7 0.25 0 0 5 0 0 0 0 0 . 70 0.5 ~ 3 5 5 0 0 0 0 0 . 125 0 1 5 5 0 0 0 0 71 0.5 1 4 5 5 0 0 0 0 71 O . 125 0 1 5 5 O 0 0 0 73 D .,5 O 1 5 5 O O O O
74 0.5 0 3 5 5 0 0 0 0 0.5 0 3 5 5 0 0 0 0 76 0.5 O 2 5 5 0 0 0 0 84 1.0 O 5 5 5 0 0 0 0 i ~ _ __ ~

- 81 - 1 ~ 80~ 68 Example 24 The post-emergent herbicidal activity of the compounds of the invention formulated as de~cribed in Example 2~ was assessed by ~he following procedure.
m e seeds of the test ~pecies were ~own in rows 2 cm deep in soil contained in seed boxes. The mono-cotyledonous plantc and the dicotyledonous plants were ~own in separate seed boxes in duplicate. The four eeed boxes were placed in a glasshouse, lightly watered with an overhead spray to initiate germination and then sub-irrigated as reguired ~or optimum plant growth.
After the plants had grown to a height of about 10 to 12.5 cm one box of each of the monocotyledonous plants and the dicotyledonous plants was removed from the glasshouse and sprayed with the required quantity of a composition of ~he in~ention. After spraying the b~xes were returned to the ylass house for a further 3 weeks and the effect of treatment was ~isually assecsed by co~parison with the untreated controls. The re~ults are presented in Table 6 where the damage to plants is ra~ed on a scale of from O to 5 where O represents from 0 to 10% damage, 1 represents ~rom 11 to 30% damage, 2 represents from 31 to 60~ damage, 3 represents from 61 to 80% damage, 4 represe~ts from 81 to 99~ damaqe and 5 represents 100% kill. A dash (-) ~eans that no experi-ment was carr~ed out.
The names of the test plants are a6 ~ollows:
Wh Wh~at Ot Wild Oats Rg Ryegrass ~m Japanese mullet P Peas Ip Ipomea M~ Mustard Sf Sunflower - 8~ _ 12~307g~j~

POST-EMERGENOE HERBICIDAL ACTIVI~Y
! - ~
TEST PI~NT
pNmO-d P~ate (kg/ha~ -- Ot Rg ;Im -- Ip MS Sf _ _ _ 1 2.0 1 5 5 5 0 0 ~ 0 1 0.5 0 3 4 4 0 0 0 0 2 2.0 1 4 5 5 0 0 0 0 2 0.5 0 2 4 5 0 0 0 0 3 2.0 O 3 5 5 0 0 0 0 2.0 3 2 5 5 0 0 0 ~ 0 0.5 0 4 4 4 0 0 0 0 6 2.0 3 5 5 5 0 0 0 0 . 6 0.5 O 4 5 5 O 0 0 0 7 2.0 2 5 5 5 0 0 9 0 , 7 0.5 2 5 S 5 0 0 0 0 7 0.25 0 5 5 5 0 0 0 0 7 0.125 O 5 5 4 0 O O 0 8 2.0 ~ 5 5 S ~ ~ 0 0 8 0.5 0 3 5 5 0 0 0 0 11 2.0 0 4 5 5 0 0 0 0 11 0.5 0 3 3 4 O 0 O 0 2.0 1 5 5 5 0 0 0 0 0.5 1 5 5 5 0 O 0 0 0.25 0 ~ 5 , 5 0 0 0 0 0.125 0 5 5 4 0 0 0 0 TABL 6 con ti nue d POST-EMERGENCE HERBICIDAL ACTIVITY

Com- APPLICATION TEST PLANT
pound Rate (kg/ha) _ No Wh Ot Rg Jm P Ip Ms S f _ , . _ _ __ 16 2.0 4 5 5 5 0 0 0 0 16 0.5 2 5 5 5 0 0 0 0 1~ 2.0 5 5 5 5 0 0 0 0 18 0.5 3 5 5 5 0 0 0 0 19 2.0 ~ 5 5 5 0 0 0 0 19 0.5 0 5 5 5 0 0 0~ 0 22 1.0 0 5 5 5 0 0 0 0 22 0.25 0 5 5 5 0 U 0 0 24 2.0 3 5 5 5 0 0 0 0 24 0.5 0 5 5 4 0 0 0 1.0 2 5 5 5 0 0 0 0 2~ 0 . 25 0 5 5 5 0 0 0 26 1 . 0 0 5 5 5 0 0 0 0 26 0 .25 0 4 5 4 0 0 0 0 28 1.0 0 5 5 5 0 0 0 0 28 0 . 25 0 5 5 4 0 0 0 0 36 1.0 2 5 5 5 0 0 0 0 36 0.25 0 5 5 5 0 0 0 0 38 2.0 3 5 5 5 0 0 0 0 3~ 0.5 1 5 4 4 0 0 0 0 39 1.0 2 5 5 5 0 0 0 0 39 0 .25 0 5 5 5 0 0 0 0 1.0 3 5 5 5 0 0 0 0 ~0 0.25 0 5 5 5 0 0 0 0 3~8~76~3 T~BLE 6 continued POST-EMERGENCE HERBICIDAL ACTIVITY
_ - : - _ TEST PLANT
poumnd Rate lkg/ha) ~ _ _ _ _ _ No Wh Ot Rg Jm P Ip Ms Sf ; _ _ ~0 0.125 0 4 5 5 0 0 0 0 41 1.0 0 5 5 5 0 0 0 0 41 0.25 0 4 5 5 0 0 0 0 46 1.0 4 5 5 5 0 0 0 0 46 0.25 0 5 5 5 0 0 0 0 47 2.0 3 5 5 5 0 0 0 0 47 0.5 0 5 5 5 0 0 0 0 2.0 4 5 5 5 0 0 0 0 0.5 ~ 4 5 5 0 0 0 0 51 2.0 4 5 5 5 0 0 0 0 51 0.5 0 4 5 5 0 0 0 0 52 1.0 0 5 5 5 0 0 0 0 52 0.25 0 4 5 5 0 0 0 0 53 1.0 0 5 5 5 0 0 0 0 53 0.25 0 3 4 4 0 0 0 0 54 2.0 2 5 5 5 0 0 0 0 54 0.5 0 3 4 5 0 0 0 0 0.25 5 5 5 5 0 0 0 0 0.125 3 5 5 5 0 0 0 0 57 0.25 1 5 5 5 0 0 0 0 57 0.125 1 4 4 5 0 0 0 0 58 1.0 4 5 5 5 0 0 0 0 5a 0.25 3 5 5 5 0 0 0 0 59 1.0 5 5 5 5 0 0 0 0 S9 0.25 3 5 5 5 0 0 0 0 ~Z~30768 .-- 85 --TABLE 6 continued POST-EMERGENCE HERBICIDAI, ACTIVITY
_ , TEST PLANT
pound Rate (kg/ha) _ ¦ Ot I Rg Jm _ Ip ~ Sf . _ 2.0 5 5 5 5 0 0 0 0 0.5 3 5 5 5 0 0 0 0 61 1.0 3 5 5 5 0 0 0 0 61 0.25 1 5 5 5 0 0 0 0 62 1.0 5 5 5 5 0 0 0 0 62 0.25 2 5 5 5 0 0 0 0 62 0.125 1 5 5 5 0 0 0 0 63 1.0 0 5 5 5 0 0 0 0 63 0.25 0 4 4 4 0 0 0 0 64 2.0 0 5 5 5 0 0 0 0 64 0.5 1 5 5 5 0 0 0 0 66 2.0 2 5 5 5 0 0 0 0 66 ~.5 0 5 5 5 0 0 0 0 67 1.0 ~ 5 5 5 0 0 0 0 67 0.25 0 4 4 4 0 0 0 0 0.5 4 5 5 5 0 0 0 0 0.125 0 4 3 5 0 0 0 ~
71 0.5 0 5 5 5 0 0 0 0 71 0.125 0 3 5 5 0 0 0 0 72 0.5 1 5 5 5 0 0 0 0 72 0.125 0 5 5 5 0 0 0 0 73 0.5 0 4 5 5 0 0 0 0 73 0.125 0 4 5 5 0 0 0 0 74 0.5 0 4/5 5 5 0 0 0 0 74 0.125 0 4/5 5 5 0 0 0 0 . __ _ - 86 ~ 8~76~3 TABLE 6 - continued POST-EMERGENCE hERBICIDAL ACTIVITY
-_ _ _ TES T PLANT
Com- APPLICATION _ _ _ pound Rate (kg/ha) Wh Ot Rg Jm P Ip ~s Sf , _ __ __ _ 0.5 0 4 5 5 0 0 0 ~
0. 125 0 3 4 5 0 0 0 0 76 0.5 2 2 5 5 0 0 0 0 76 0 . 125 0 0 5 5 0 0 0 0 84 0.125 O 2 1 ~ 0; 0 0 0 ~ . . _ - 8 7 _ 1.2 80~6~3 Example 2 5 The comp~unds were formulated ~or test by mixing an appropriate amount with 5 ml of an emulsion prepared by dilutinq 160 ml of a solution containing 21.9 g per litre of ~Span" 80 and 78.2 q per litre of ~Tween" 20 in methylcyclohexanone to 500 ml with water.
"Span~ 80 is a Trade Mark for a surface-active aqent comprising sorbitan monolaurate. ~Tween~ 20 is a Trade Mark for a surface-active agent comprising a condensate of sorbitan monolaurate with 20 molar proportions of ethylene oxide. Each 5 ~1 emulsion containinq a test compound was then diluted to 40 ml with water and sprayed on to young pot plants (post-emergence test) of the species named in Table 7 below. Damage ~o test li plants was assessed after 14 days on a scale of 0 to 5 where 0 i5 0 to 20% damaqe and 5 is complete kill.
In a test for pre-emergence herbicidal activitv, seeds of the test plants were sown in a shall~w slit formed in the surface of soil in fibre trays. The ~urface was then levelled and sprayed, and fresh soil then spread thinlv o~er the s~rayed surface. Assessment of herbi-cidal damage was carried out after 21 days using the ~ame scale of 0 to 5 as the post-emergence test. In both cases the degree of herbicidal damaqe was assessed 25 ~y comparison with untreated control plants. The re-~ults are given in Ta~le 7 below. A dash (-) means that no experiment wa~ carried out.
The names of the test plants were as follows:
Sb Sugar beet Rp Rape Ct Cotton Sy S~y bean Mz Maize Ww Winter wheat Rc Rice Sn Sene~io w lgaris Ip Ipomea ~rpurea - 8 8 ~ 768 ~n ~naranthus retrofl~xu~
Pi ~ avicul~re Ca enopodium album Ga Galium aparine Xa Xanthium pensylvanicum Ab Abutilon theoPhrasti Co Cassia obtusifolia Av Avena fatua Dg Digitaria san~uinalis Al Alopecurus myosuroides St Setaria viridis Ec Echinochloa crus-galli Sh Sor~hum halepense Ag ~9EY~Y~ repens Cn ~yperus rotundas - 89 ~ 307~8 TEST PhANT
COm_ APPLI CAT I ON _I
pour~d MethOd Rate . _ _ __ __ ~ __ NO (kg/ha) Sb RP Ct ¦~ Z WW Rc Sn IP Am ~ CE

7 POST 1 . 9 0 0 0 _ 5 3 4 0 0 _ 0 0 7 POS~ 0 .5 0 0 0 _ 5 0 4 0 1 _ 0 0 POST ~.0 _ ~ _ _ _ 2 _ _ _ _ _ _ POST 1 " 0 _ _ _ _ _ 1 _ _ _ _ _ POST 0 . 5 _ _ _ _ _ 0 _ _ _ _ POST O . 2 5 _ _ _ _ _ 0 _ _ _ _ _ 11 POST 2 . 0 _ _ _ _ _ 1 _ . _ _ 11 POST 1. 0 _ _ _ _ _ 1 _ _ _ _ _ 11 POST 0.5 _ _ _ _ _ U _ _ _ _ _ _ 11 POST 0 . 25 _ _ _ _ O _ _ _ _ _ ~LZ~ ;8 TABLE 7 -~ PART B
_ _ _ . ~
Com- APPLICATION TEST PLANT
pound ~!ethod Ra~e _ _ ~ _ _ _ _ _ No (kg/ha) Ga Xa Ab Co Av Dg Al St Ec Sh Ag C
~ _ _ _ _ __ _ __ _ __ 7 POST 1. 9 0 0 0 0 5 3 5 4 5 4 2 0 7 POST 0.5 0 0 0 0 4 3 4 5 5 3 0 0 POST 2 . 0 _ _ _ _ 5 _ 4 5 _ _ _ POST 1. 0 _ _ _ _ 4 _ 4 4 _ _ _ POST 0.5 _ _ _ _ 4 _ 4 3 _ _ _ _ POST 0.25 _ _ _ _ 4 _ 4 3 _ _ _ _ 11 POST 2 . 0 _ _ _ _ 5 _ 4 4 _ _ _ 11 POST 1. 0 _ _ _ _ 4 _ 4 4 _ _ _ 11 POST 0 . 5 _ _ _ _ 4 _ 4 4 _ _ _ 11 POST 0 . 2 5 _ _ _ _ 4 _ 4 3 _ _ _ _ ,, _ ......... ~ __ _ __ _ _ _ - 91 ~ 7~8 Example _ This Example illustrates the selective herbicidal activity of compounds of the invention.
The compounds were formulated for test by mixing an appropriate amount with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.8 g per litre of "Span" 80 and 78.2 g per litre of "Tween" 20 in methylcyclohexanone to 500 ml with water. "Span" 80 is a Trade Mark for a surface-active agent comprising sorbitan monolaurate. nTween" 20 is a Trade Mark for a surface-active agent comprising a condensate or sorbitan monolaurate with 20 molar proportions of ethylene oxide.
Each 5 ml emulsion containing a test compound was then - diluted ~o 40 ml with water and sprayed on to young pot plants (post-emergence test) of the species named in Table 8 below. Damage to test plants was assessed after 26 days on a scale of 0 to 9 where 0 is 0 to 10% damage and 9 is complete kill. The degree of herbicidal damage was assessed by comparison with un~reated control plants and the results are given in Table 8 below. A dash (-) means that no experiment was carried out.
The names of the test plants were as follows:
Ww - winter wheat Br - spring barley Av - Avena fatua Al - Alopecurus m~osuroides St - Setaria viridis . ~ - 92 - ~.X~ 1768 POST-EMERGENCE HERBICIDAI ACTIVITY
_ TEST PL~IT
pom~d Ra te ( k g/h a ) No Ww BrA~ Al S t _ _ _ 0.10 0 09 8 6 0.20 1 19 9 8 0.40 0 19 9 9 7 0.03 0 18 8 8 7 0.04 0 09 9 8 7 0 .08 1 1_ _ 7 0.16 0 1_ _ 0.04 0 19 9 8 0.08 1 2_ _ 0 . 16 2 5_ _ 0.08 0 19 6 7 0 . 16 1 1_ _ 0.32 1 0_ _ 18 0.03 0 19 9 8 18 0.04 0 19 8 8 18 0.08 _ _9 9 9 18 0.16 0 0_ _ _ 0.04 _ _9 8 9 0 . 06 0 69 8 9 0.08 0 59 8 9 0.16 0 8_ _ 0.32 0 9_ _ ~ _ ` ~ 93 ~80~76~3 _ TABLE 8 Continued -POST-EMERGENCE HERBICIDAL ACTIVITY

TEST PLANT
Com- APPLICATION ~_ _ _ pNuOnd Rate (kg/ha) Ww Br Av Al St , 62 0.02 _ _ 9 7 9 62 0.04 _ _ 9 9 9 62 0.06 O 5 9 9 9 62 0.08 O 7 9 9 9 62 0.16 O 9 _ _ 62 0.32 O 9 _ _ 72 0.04 _ _ 9 9 9 72 0.06 O O 9 9 9 72 0.08 O 3 9 9 9 72 0.16 O 7 _ _ 72 0.32 1 9 _ _ 78 0.04 _ _ 9 7 8 78 0.06 ~ O 9 8 9 78 O.OB O 2 9 9 9 78 0.16 O 7 _ _ 78 0.32 O 9 _ _ _ ~ .. . l

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A compound of formula:- wherein E is selected from hydrogen and R3CO-, and R3 is selected from the group consisting of C1 to C6 alkyl, C1 to C6 fluoroalkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, and phenyl; and n is an integer chosen from 2 to 5.
2. A compound according to Claim 1 wherein E is hydrogen.
3. A compound according to Claim 1 wherein R3 is selected from the group consisting of C1 to C6 alkyl, C1 to C6 fluoroalkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, and phenyl.
4. A compound according to Claim 3 wherein R3 is C1 to C6 alkyl-5. A compound according to Claim 4 wherein R3 is selected from ethyl and n-propyl.